CN101302233A - Preparation of pentaerythritol diphosphonate melamine salt - Google Patents
Preparation of pentaerythritol diphosphonate melamine salt Download PDFInfo
- Publication number
- CN101302233A CN101302233A CNA200810016971XA CN200810016971A CN101302233A CN 101302233 A CN101302233 A CN 101302233A CN A200810016971X A CNA200810016971X A CN A200810016971XA CN 200810016971 A CN200810016971 A CN 200810016971A CN 101302233 A CN101302233 A CN 101302233A
- Authority
- CN
- China
- Prior art keywords
- pentaerythritol diphosphonate
- preparation
- reaction
- melamine salt
- diphosphonate melamine
- 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
Abstract
The invention relates to a method for making pentaerythritol diphosphonate melamine salt, belonging to the synthesis technical field. The making process at least comprises two steps, i.e. synthesis and post treatment. Pentaerythritol diphosphonate diphosphoryl chloride, reaction accelerant, melamine and water are reacted at a temperature higher than 60 DEG C, and then are made into pentaerythritol diphosphonate melamine salt through cooling, scrubbing, filtration and drying. The pentaerythritol diphosphonate melamine salt made by the method has excellent compatibility with polymer and outstanding flame retardant property, and belongs to nontoxic, low-smoke and efficient environment-friendly fire retardant. Moreover, the method can effectively reduce reaction temperature and increase reaction yield without generating organic pollution along with simple process, high production efficiency and low energy consumption.
Description
One, technical field
The invention belongs to synthesis technical field, relate to the fire retardant technology of preparing, particularly the expansion type flame retardant technology of preparing.
Two, background technology
Phosphorus-nitrogen expanding fire retardant is not halogen-containing, with phosphorus, nitrogen, carbon is main component, P-N cooperative flame retardant effect can take place when being heated, generate the carbonaceous foam layer of even compact, heat insulation, oxygen barrier, press down cigarette, and can prevent to produce molten drop, and have the good flame performance, meet the development trend that requires the few cigarette of fire retardant, low toxicity now.
The monomer expansion type flame retardant is that acid source, charcoal source and source of the gas three parts that will form mixed expanded type fire retardant are combined in the molecule, fundamentally solve fire retardant each several part interreaction in the fire-retardant process of material, fire retardant is composite and composite flame retardant system in problem such as each component skewness, help bringing into play nitrogen, phosphorus synergistic fire retardation, and molecular weight is big, Heat stability is good, water tolerance, resistance to migration are good.
The expansion type flame retardant pentaerythritol diphosphonate melamine salt of nitrogenous phosphorus (being called for short TODPDM) is present unique industrialized monomer expansion type flame retardant, and its structure is as follows:
Fire retardant TODPDM is a white solid, is slightly soluble in water, is insoluble to organic solvents such as alcohol, ketone, ether, hydrocarbon, halohydrocarbon.Decomposition temperature is greater than 250 ℃, have Heat stability is good, whiteness height, durable, fast light, nontoxic, with advantages such as compatible polyolefin is good.
The preparation method of fire retardant TODPDM is generally by pentaerythrite diphosphate ester two phosphoryl chlorides (3,9-two chloro-2,4,8,10-four oxos-3,9 hosphospiro-3,9-dioxy [5,5] undecane) and trimeric cyanamide prepared in reaction at present.The structure of pentaerythrite diphosphate ester two phosphoryl chlorides is as follows:
The operational path of bibliographical information has following several:
(1) pentaerythrite diphosphate ester two phosphoryl chlorides, trimeric cyanamide, water are mixed together and are heated to backflow, react 15-50 minute, generate fire retardant TODPDM, this is simple for process, be maximum method of using at present, but synthetic yield is low, the bibliographical information productive rate is at 72-82%.(Yuval Halpen, US4154930,1979; Ou Yuxiang, Li JianJun, fire retardant-performance, preparation and application, Chemical Industry Press, 2006, p260; Zhu Guangjun, Liu Guitao, Wang's letter, Yang Xujie, land route moral, fire retardant material and technology, 2003, (5), 3)
(2) hydrolysis in alkali of pentaerythrite diphosphate ester two phosphoryl chlorides generates organic acid, trimeric cyanamide and inorganic acid reaction are made melamine salt, again organic acid and trimeric cyanamide reactant salt are generated fire retardant TODPDM, and this technological process is complicated, need to consume alkali and mineral acid, productive rate about 84%.(Yuval?Halpen，US4154930，1979)
(3) pentaerythrite diphosphate ester two phosphoryl chloride hydrolysis generate organic acid and HCl, HCl removes with hydrolysate, again organic acid and trimeric cyanamide reaction are generated fire retardant TODPDM, this process yield is higher, productive rate 80-95%, but the HCl subtractive process increases the reaction times, and easily causes the further hydrolysis of intermediate hydrolysate, reduces the fire retardant productive rate.(Fang Chenpeng thanks and flies Mu Changjiang, Chinese publication CN 1824731A, 2006 for Yang Hui, all arrows)
(4) with the triethylamine be acid binding agent, pentaerythrite diphosphate ester two phosphoryl chlorides and trimeric cyanamide heating reflux reaction 10 hours in dichloromethane solvent, product yield about 86%, this method with an organic solvent, and long reaction time.(Lv Tong, Wu Zanmin, Han Wei, Wen Yuanmei, plastics industry, 2001,29 (1), 1)
In sum, the technology of preparing of monomer expansion type flame retardant TODPDM exists synthetic yield low, and long reaction time or need problems such as organic solvent, so cost height have hindered its large-scale marketing.
Three, summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of phosphorus-nitrogen expanding fire retardant pentaerythritol diphosphonate melamine salt is provided, and the synthetic yield that prior art exists is low to overcome, long reaction time, need problems such as organic solvent, product cost height.
The preparation method of the fire retardant pentaerythritol diphosphonate melamine salt that the present invention relates to, preparation process comprise synthetic and two steps of aftertreatment at least:
(1) building-up process: pentaerythrite diphosphate ester two phosphoryl chlorides, reaction promotor, trimeric cyanamide, water are added in the reactor, be warming up to more than 60 ℃, reacted 5-60 minute, reaction is finished postcooling to room temperature, being washed with water to does not have chlorion in the filtrate, filter, and obtains solid product A.
(2) last handling process: dry solid product A obtains target fire retardant pentaerythritol diphosphonate melamine salt.
The preparation method of the fire retardant pentaerythritol diphosphonate melamine salt that the present invention relates to, the feed way of described building-up process is earlier pentaerythrite diphosphate ester two phosphoryl chlorides, trimeric cyanamide, water to be added in the reactor, be warming up to more than 60 ℃ and reacted 0-20 minute, add reaction promotor again and react.
The preparation method of the fire retardant pentaerythritol diphosphonate melamine salt that the present invention relates to, finish synthetic back and in last handling process, with the surface-modifying agent aqueous solution filtration product A is carried out surface treatment earlier, obtain the fire retardant of surface treatment pentaerythritol diphosphonate melamine salt after the drying.
The preparation method of the fire retardant pentaerythritol diphosphonate melamine salt that the present invention relates to, described reaction promotor is selected from the mixed system of one or more the mated uses in triethylamine, trolamine, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide, the ammoniacal liquor.
The preparation method of the fire retardant pentaerythritol diphosphonate melamine salt that the present invention relates to, described temperature of reaction are preferred more than 75 ℃, 10-40 minute.
The preparation method of the fire retardant pentaerythritol diphosphonate melamine salt that the present invention relates to, the consumption of described reaction promotor is that the mol ratio of reaction promotor and trimeric cyanamide is between 0.5-1.2.
The preparation method of the fire retardant pentaerythritol diphosphonate melamine salt that the present invention relates to can effectively reduce temperature of reaction, improves reaction yield, does not produce organic contamination; Technology is simple, the efficient height, and energy consumption is low.
Fire retardant and the polymer phase capacitive of the preparation method of the fire retardant pentaerythritol diphosphonate melamine salt that employing the present invention relates to preparation are good, and flame retardant properties is good, belong to nontoxic, hang down cigarette, environment friendly flame retardant efficiently.
Four, embodiment
Below by embodiment the technical scheme that the present invention relates to is described further, but not as limiting the scope of the invention.
Embodiment one
Get 4.3g Na
2CO
3, 11.88g pentaerythrite diphosphate ester two phosphoryl chlorides, 10.08g trimeric cyanamide, 80mL water add in the there-necked flask of belt stirrer, prolong, thermometer, be heated to backflow, stirring reaction 10min, stopped reaction, be cooled to room temperature, filter, washing filtration product with water does not have chlorion four times to filtrate, drying obtains white solid 18.8g, productive rate 91.8%.
Embodiment two
Get in the there-necked flask of 6.0g trolamine, 5.94g pentaerythrite diphosphate ester two phosphoryl chlorides, 4.91g trimeric cyanamide, 40mL water adding belt stirrer, prolong, thermometer, be heated to 80 ℃, stirring reaction 30min, stopped reaction, be cooled to room temperature, filter, washing filtration product with water does not have chlorion six times to filtrate, drying obtains white solid 9.0g, productive rate 89.0%.
Embodiment three
Get in the there-necked flask of 12mL ammoniacal liquor, 29.7g pentaerythrite diphosphate ester two phosphoryl chlorides, 25.2g trimeric cyanamide, 250mL water adding belt stirrer, prolong, thermometer, be heated to 60 ℃, stirring reaction 60min, stopped reaction, be cooled to room temperature, filter, washing five times with water does not have chlorion to filtrate, filtration product is added in the 150mL 1wt% sodium dodecyl benzene sulfonate aqueous solution, 50 ℃ are stirred 30min, are cooled to room temperature, filter, drying obtains white solid 46.5g, productive rate 90.8%.
Embodiment four
Get in the there-necked flask of 5.94g pentaerythrite diphosphate ester two phosphoryl chlorides, 5.04g trimeric cyanamide, 50mL water adding belt stirrer, prolong, thermometer, be heated to 80 ℃, stirring reaction 5min, add the 5.6mL triethylamine and continue reaction 30min, stopped reaction, be cooled to room temperature, filter, washing five times with water does not have chlorion to filtrate, filtration product is added in the 30mL 1wt% lauryl sodium sulfate aqueous solution, and 80 ℃ are stirred 30min, be cooled to room temperature, filter, drying obtains white solid 9.6g, productive rate 93.8%.
Embodiment five
Get in the there-necked flask of 11.88g pentaerythrite diphosphate ester two phosphoryl chlorides, 10.34g trimeric cyanamide, 50mL water adding belt stirrer, prolong, thermometer, be heated to backflow, stirring reaction 10min adds 50mL 20wt% KHCO
3The aqueous solution continues reaction 10min, stopped reaction, be cooled to room temperature, filter, washing four times with water does not have chlorion to filtrate, filtration product is added in the 30mL 1wt% lauryl sodium sulfate aqueous solution, 80 ℃ are stirred 30min, are cooled to room temperature, filter, drying obtains white solid 18.2g, productive rate 87.8%.
Embodiment six
Get in the there-necked flask of 29.7g pentaerythrite diphosphate ester two phosphoryl chlorides, 26.3g trimeric cyanamide, 150mL water adding belt stirrer, prolong, thermometer, be heated to 70 ℃, stirring reaction 15min adds the 55mL 8wt%NaOH aqueous solution and 34mL 20wt%NaHCO
3The aqueous solution continues reaction 50min, and stopped reaction is cooled to room temperature, filters, washing five times with water does not have chlorion to filtrate, filtration product, 1g sodium stearate are added in the 150mL water, and 80 ℃ are stirred 30min, are cooled to room temperature, filter, drying obtains white solid 47.4g, productive rate 90.2%.
Claims (6)
- The preparation method of 1 one kinds of pentaerythritol diphosphonate melamine salts comprises synthetic and two steps of aftertreatment at least, it is characterized in that:(1) building-up process: pentaerythrite diphosphate ester two phosphoryl chlorides, reaction promotor, trimeric cyanamide, water are added in the reactor, be warming up to more than 60 ℃, reacted 5-60 minute, reaction is finished postcooling to room temperature, being washed with water to does not have chlorion in the filtrate, filter, and obtains solid product A.(2) last handling process: dry solid product A obtains target fire retardant pentaerythritol diphosphonate melamine salt.
- The preparation method of the described pentaerythritol diphosphonate melamine salt of 2 claims 1, the feed way that it is characterized in that building-up process is for adding pentaerythrite diphosphate ester two phosphoryl chlorides, trimeric cyanamide, water in the reactor earlier, be warming up to more than 60 ℃ and reacted 0-20 minute, add reaction promotor again and react.
- The preparation method of the described pentaerythritol diphosphonate melamine salt of 3 claims 1 is characterized in that last handling process carries out surface treatment with the surface-modifying agent aqueous solution to filtration product A earlier, and drying obtains pentaerythritol diphosphonate melamine salt again.
- The preparation method of 4 claims 1,2 or 3 described pentaerythritol diphosphonate melamine salts, described reaction promotor is selected from the mixed system of one or more the mated uses in triethylamine, trolamine, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide, the ammoniacal liquor.
- The preparation method of 5 claims 1,2 or 3 described pentaerythritol diphosphonate melamine salts, described reaction conditions is more than 75 ℃, 10-40 minute.
- The preparation method of 6 claims 1,2 or 3 described pentaerythritol diphosphonate melamine salts, the mol ratio of described reaction promotor and trimeric cyanamide is between 0.5-1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810016971XA CN101302233B (en) | 2008-06-27 | 2008-06-27 | Preparation of pentaerythritol diphosphonate melamine salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810016971XA CN101302233B (en) | 2008-06-27 | 2008-06-27 | Preparation of pentaerythritol diphosphonate melamine salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101302233A true CN101302233A (en) | 2008-11-12 |
| CN101302233B CN101302233B (en) | 2012-07-18 |
Family
ID=40112347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810016971XA Expired - Fee Related CN101302233B (en) | 2008-06-27 | 2008-06-27 | Preparation of pentaerythritol diphosphonate melamine salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101302233B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914208A (en) * | 2010-08-19 | 2010-12-15 | 中国科学技术大学 | Phosphorus-containing and nitrogen-containing expansion type flame-retardant polymer and preparation method thereof |
| CN102585135A (en) * | 2012-03-05 | 2012-07-18 | 中北大学 | Reactive intumescent flame retardant for polyurethane and synthesis method of reactive intumescent flame retardant |
| CN101638421B (en) * | 2009-08-25 | 2012-10-03 | 安徽中鼎密封件股份有限公司 | Preparation method of o-diaminobenzene phosphorylchloride condensed pentaerythritol ester |
| CN108329519A (en) * | 2018-01-31 | 2018-07-27 | 福建师范大学 | A kind of polyhydroxy phosphate flame retardants and the preparation method and application thereof |
| CN108659047A (en) * | 2018-05-15 | 2018-10-16 | 福州大学 | A kind of preparation method of boracic one pack system expansion type flame retardant |
| CN109705634A (en) * | 2019-01-15 | 2019-05-03 | 安徽大学 | A kind of concave convex rod soil matrix composite flame-retardant agent and its preparation and application with the modification of Nitrogen-and Phosphorus-containing organic matter |
-
2008
- 2008-06-27 CN CN200810016971XA patent/CN101302233B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101638421B (en) * | 2009-08-25 | 2012-10-03 | 安徽中鼎密封件股份有限公司 | Preparation method of o-diaminobenzene phosphorylchloride condensed pentaerythritol ester |
| CN101914208A (en) * | 2010-08-19 | 2010-12-15 | 中国科学技术大学 | Phosphorus-containing and nitrogen-containing expansion type flame-retardant polymer and preparation method thereof |
| CN101914208B (en) * | 2010-08-19 | 2012-07-25 | 中国科学技术大学 | Phosphorus-containing and nitrogen-containing expansion type flame-retardant polymer and preparation method thereof |
| CN102585135A (en) * | 2012-03-05 | 2012-07-18 | 中北大学 | Reactive intumescent flame retardant for polyurethane and synthesis method of reactive intumescent flame retardant |
| CN102585135B (en) * | 2012-03-05 | 2013-08-07 | 中北大学 | Reactive intumescent flame retardant for polyurethane and synthesis method of reactive intumescent flame retardant |
| CN108329519A (en) * | 2018-01-31 | 2018-07-27 | 福建师范大学 | A kind of polyhydroxy phosphate flame retardants and the preparation method and application thereof |
| CN108659047A (en) * | 2018-05-15 | 2018-10-16 | 福州大学 | A kind of preparation method of boracic one pack system expansion type flame retardant |
| CN108659047B (en) * | 2018-05-15 | 2019-09-13 | 福州大学 | A kind of preparation method of boracic one pack system expansion type flame retardant |
| CN109705634A (en) * | 2019-01-15 | 2019-05-03 | 安徽大学 | A kind of concave convex rod soil matrix composite flame-retardant agent and its preparation and application with the modification of Nitrogen-and Phosphorus-containing organic matter |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101302233B (en) | 2012-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101302233B (en) | Preparation of pentaerythritol diphosphonate melamine salt | |
| CN100500657C (en) | Triazine series oligomer and its synthesizing method | |
| CN103319538A (en) | Preparation method of hexaphenoxy cyclotriphosphazene | |
| CN102093566B (en) | Macromolecular intumescent flame retardant with phosphorus and nitrogen and synthesis method thereof | |
| CN102757579A (en) | Oxa-phosphaphenanthrene flame retardant containing cyclotriphosphonitrile structure, and preparation method and application thereof | |
| CN103882698B (en) | A kind of s-triazine type fire retardant and its preparation method and application | |
| CN102336926A (en) | Expandable flame retardant modified hydrotalcite as well as preparation method and application thereof | |
| CN102120810B (en) | Preparation method of high solid content expandable melamine modified urea resin | |
| CN105924672A (en) | Dual-cage structure contained triazine-ring flame retardant with anti-oxidation function and preparation method | |
| CN102603800A (en) | Preparation method of phosphonitrile flame retardant | |
| CN107868255A (en) | The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification | |
| CN105295093A (en) | Ring phosphonitrile type additive flame retardant and preparation method thereof | |
| CN103539820A (en) | Preparation method of hexaphenoxycyclotriphosphazene | |
| CN102417596A (en) | Phosphate ester polymer intumescent flame retardant and preparation method thereof | |
| CN101570518B (en) | Preparation method for expansion type melamine hypophosphite fire retardant | |
| CN102898337A (en) | Method for producing granular flame retardant tetrabromobisphenol S ether | |
| CN108951164B (en) | Flame-retardant finishing agent for pure cotton fabric and preparation method thereof | |
| CN109054098A (en) | A kind of piperazine modified lignin resin/aluminum phosphate dual cladding red phosphorus combustion inhibitor and its application in HIPS | |
| CN109796496B (en) | Three phosphazene derivative of ring containing alkoxy and its preparation method and application | |
| CN105037426A (en) | Reactive type intumescent flame retardant and synthesis method thereof | |
| CN107021986A (en) | A kind of phenoxy phosphazene fire retardant and preparation method thereof | |
| CN101638421B (en) | Preparation method of o-diaminobenzene phosphorylchloride condensed pentaerythritol ester | |
| CN106009039A (en) | Flame-retardant agent containing spirane structure and having antioxidant function and preparation method | |
| CN109400963A (en) | A kind of preparation method of graphene-based flame-proof heat-resistant sisal cellulose film | |
| CN109897159A (en) | A kind of reactive flame retardant and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20090814 Address after: Postcode 3, Tian Jia Dong Road, Tianqiao District, Shandong City, Ji'nan Province, China: 250031 Applicant after: The 53 Research Institute of China weaponry industry group Co-applicant after: Yuyao China Plastics City Plastics Research Institute Co., Ltd. Address before: Postcode 3, Tian Jia Dong Road, Tianqiao District, Shandong City, Ji'nan Province, China: 250031 Applicant before: No.53 Inst., China Weaponry Industry Group |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120718 Termination date: 20150627 |
|
| EXPY | Termination of patent right or utility model |