CN103289124B - Phosphorus flame retardant namely 1,2-dicarboxylic ethyl diphenyl phosphine oxide and preparation method thereof as well as halogen-free flame-retardant polyester composition - Google Patents
Phosphorus flame retardant namely 1,2-dicarboxylic ethyl diphenyl phosphine oxide and preparation method thereof as well as halogen-free flame-retardant polyester composition Download PDFInfo
- Publication number
- CN103289124B CN103289124B CN201310267672.4A CN201310267672A CN103289124B CN 103289124 B CN103289124 B CN 103289124B CN 201310267672 A CN201310267672 A CN 201310267672A CN 103289124 B CN103289124 B CN 103289124B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- polyester composition
- retardant
- halogen
- phosphine oxide
- 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
Images
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a phosphorus flame retardant namely 1,2-dicarboxylic ethyl diphenyl phosphine oxide and a preparation method thereof as well as a halogen-free flame-retardant polyester composition. The phosphorus flame retardant is obtained by performing an addition reaction on raw materials including diphenyl phosphine oxide and maleic acid. Polyester PET (polyethylene terephthalate) containing the novel environment-friendly phosphorus flame retardant is excellent in flame retardant property, the flame retardant grade reaches a UL-94V-0 grade when the phosphorus content is 1.75%, and the added amount of the flame retardant is low, so that the cost is low, the influence on mechanical properties of halogen-free flame-retardant co-polyester is small. However, when the phosphorus content in the D0P0-MA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-methyl acrylate) flame retardant polyester reaches more than 1.8%, the same effect as that of the halogen-free flame-retardant polyester composition provided by the invention can be achieved.
Description
Technical field
The invention belongs to high molecular fire retardant field, relate in particular to the synthetic and halogen-free flame-retarded polyester composition of novel environment friendly reactive phosphorus flame retardant DPO-MA.
Background technology
Poly-pure terephthalic acid's second diester (PET) fiber has good physical and mechanical properties, is widely used in clothes carpet and decorates the fields such as bedclothes, becomes the widest, the maximum chemical fibre kind of consumption of range of application.But the limiting oxygen index(LOI) of PET fiber is only 21%, belong to flammable fiber, greatly limit its application, therefore need it to carry out flame-retardant modified, wherein, reactive phosphorus flame retardant is owing to participating in the polymerization process of polymkeric substance and becoming the part of polymer molecular chain, and not only flame retardant properties is superior, addition is few, and flame retardant properties is lasting, become the focus of people's research in recent years.Wherein DOPO (9, 10-dihydro-9-oxy-10-phospho hetero phenanthrene-10-oxide compound) based flame retardant, as DDP, the reactive flame retardants such as DOPO-MA are owing to containing biphenyl rigid radical, superior for heat resistance, general decomposition temperature is higher than the processing temperature 50-60 ℃ of PET, and the consumption that reaches identical flame retardant rating is less than other based flame retardants, synthetic flame retardant polyester section flame retardant properties is superior, the problem that there will not be fire retardant to separate out in the course of processing, flame retardant properties is more lasting simultaneously, particularly Flame Retardant PET Fibres washing fastness is greatly improved, therefore DOPO based flame retardant gets more and more people's extensive concerning, (the A Novel Halogen-Free Flame Retardant PBT Based On9 such as Liu, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.C.5
thinternational Symposium on Engineering Plastics, 2011) prepared DOPO-MA flame-retardant PBT polyester, when DOPO-MA content reaches 20%wt, when phosphorus content is 1.86%, flame retardant polyester PBT can pass through UL-94V-0 rank, (the epoxy resin research .J. insulating material that flame retardant type DOPO-is maleic anhydride modified such as Wang Yu, 2010,43 (3): 20-28.) prepared DOPO-MA fire retarding epoxide resin, in the time that phosphorus content reaches 2%, LOI index is 33.4%, can reach UL-94V-0 standard.But the expensive and difficult preparation of raw material DOPO of synthetic DOPO based flame retardant, preparation process can pollute, and this has limited the large-scale application of DOPO based flame retardant.
Summary of the invention
The object of the invention is to the shortcoming for the existence of existing DOPO based flame retardant, provide a kind of cost of material reasonable, consumption is few, and preparation technology's environmental protection is simple, is easy to industrialized fire retardant.
Another object of the present invention is to provide the halogen-free flame-retarded polyester composition that contains above-mentioned fire retardant, flame retardant rating reaches UL94V-0 rank.
To achieve the above object of the invention, the chemical name of phosphorus flame retardant of the present invention is:
1,2-dicarboxyl ethyl diphenyl phosphine oxide, referred to as DPO-MA: its molecular structural formula is:
Phosphorus flame retardant 1 of the present invention, 2-dicarboxyl ethyl diphenyl phosphine oxide is to carry out addition reaction take diphenyl phosphine oxide and toxilic acid as raw material, reaction scheme is:
Preparation method is in detail:
First pass into nitrogen excluding air to reactor, then in reactor, add diphenyl phosphate oxidation and solvent, and add a small amount of phase-transfer catalyst, be warming up to again 60 ℃, then slowly add toxilic acid, control temperature of reaction between 60-80 ℃, reaction is after 2-4 hour, filtration obtains white solid, obtains white powder be product by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice;
Described solvent is one or more in benzene class, ester class, alkyl chloride hydro carbons;
Described solvent load is 1.5-3 times of diphenyl phosphine oxide quality;
Described diphenyl phosphine oxide and the mol ratio of toxilic acid are 1:(1-1.2);
Described phase-transfer catalyst is tetrahydrofuran (THF) or pyridine, and consumption is 3%～5% of diphenyl phosphine oxide quality.
Described benzene and tetrahydrofuran (THF) mixed solution are 2:1 preparation in mass ratio.
Owing to containing two carboxyls in the flame retardant molecule described in the present invention, can participate in the polyreaction of PET, be linked on the skeleton of PET, form the PET with lasting flame retardant resistance.
The preparation method of halogen-free flame-retarded polyester composition of the present invention is as follows,
The first step: raw material is prepared
Take fire retardant DPO-MA, pure terephthalic acid's (being called for short TPA), ethylene glycol (EG), catalyst Ti acid butyl ester and stablizer, wherein:
The adding proportion of described fire retardant DPO-MA is the 9%-21% of the each component gross weight of flame retardant polyester composition;
Described catalyzer adding proportion is 0～0.05% of the each component gross weight of flame retardant polyester composition;
Described stablizer is triphenyl phosphite or trimethyl phosphite 99; Stablizer adding proportion is 0～0.05% of the each component gross weight of flame retardant polyester composition.
Second step: the copolymerization of halogen-free flame-retarded polyester composition
Be (1.5～1.8) in molar ratio by EG and TPA: 1 adds in reactor, and adds fire retardant DPO-MA, passes into N in reactor
2be warming up to 230 ℃ and remain to esterification yield and reach 96%, then in reactor, add catalyzer and stablizer, then be warming up to 270 ℃, in 45min, be slowly decompressed to <10mmHg and keep reaction 2h to obtain halogen-free flame-retarded polyester composition.
Compared with traditional DOPO based flame retardant, tool of the present invention has the following advantages:
(1) DPO-MA contains the similar structure with DOPO, contains equally phenyl ring rigid structure, and compared with DOPO, the raw material diphenyl phosphine oxide of DPO-MA has the price lower than DOPO, higher phosphorus content.
(2) this fire retardant can participate in the polyreaction of PET, the halogen-free antiflaming polyester PET section making, flame retardant properties is superior, in the time of 1.75% left and right that phosphorus content is flame-proof copolyester, flame retardant rating reaches UL94V-0 level, and the section of halogen-free flame-proof copolymerized ester can keep good mechanical property.And the above same effect that just can reach of the general phosphorus content to 1.8% of DOPO-MA fire retardant polyester.
Accompanying drawing explanation
Fig. 1 is the infrared spectra of DPO-MA in the embodiment of the present invention 1;
Fig. 2 is the nuclear-magnetism H spectrum of DPO-MA in the embodiment of the present invention 1.
Embodiment
Describe technical scheme of the present invention in detail with specific embodiment with reference to the accompanying drawings below; Wherein:
Embodiment 1-11 is the object lesson of fire retardant DPO-MA of the present invention;
Embodiment 12-17 utilizes fire retardant DPO-MA of the present invention to prepare the object lesson of halogen-free flame-retarded polyester composition.
Embodiment 1
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 45g benzene are joined in reactor, and add 0.8g tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 11.6g (0.1mol) toxilic acid, keep 70 ℃ of temperature of reaction, react after 2 hours, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 91%, the infrared spectra of synthetic fire retardant DPO-MA and nuclear-magnetism H spectrogram are shown in respectively Fig. 1 and Fig. 2.
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 45g benzene are joined in reactor, and add 0.8g tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 12.2g (0.105mol) toxilic acid, keep 70 ℃ of temperature of reaction, react after 2 hours, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 98%.
Embodiment 3
Embodiment 3 concrete technologies are as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 45g benzene are joined in reactor, and add 0.8g tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 12.76g (0.11mol) toxilic acid, keep 70 ℃ of temperature of reaction, react after 2 hours, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 98%.
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 45g benzene are joined in reactor, and add 0.8g tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 12.2g (0.105mol) toxilic acid, keep 60 ℃ of temperature of reaction, react after 2 hours, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 87%.
Embodiment 5
Embodiment 5 concrete technologies are as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 45g benzene are joined in reactor, and add 0.8g tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 12.2g (0.105mol) toxilic acid, keep 80 ℃ of temperature of reaction, react after 2 hours, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 98%.
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 45g benzene are joined in reactor, and add 0.8gml tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 12.2g (0.105mol) toxilic acid, keep 70 ℃ of temperature of reaction, react after 1 hour, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 78%.
Embodiment 7
Embodiment 7 concrete technologies are as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 45g benzene are joined in reactor, and add 0.8g tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 12.2g (0.105mol) toxilic acid, keep 70 ℃ of temperature of reaction, react after 3 hours, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 96%.
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 45g ethylene dichloride are joined in reactor, and add 0.8g tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 12.2g (0.105mol) toxilic acid, keep 70 ℃ of temperature of reaction, react after 2 hours, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 98%.
Embodiment 9
Embodiment 9 concrete technologies are as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 45g ethyl acetate are joined in reactor, and add 0.8g tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 12.2g (0.105mol) toxilic acid, keep 70 ℃ of temperature of reaction, react after 2 hours, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 98%.
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 35g ethyl acetate are joined in reactor, and add 1ml tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 12.2g (0.105mol) toxilic acid, keep 70 ℃ of temperature of reaction, react after 2 hours, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 93%.
Embodiment 11
Embodiment 11 concrete technologies are as follows:
Mechanical stirring, thermometer, reflux condensing tube, N are being housed
2in the dry four-hole boiling flask of 250ml of conduit, pass into drying nitrogen and get rid of the air in flask, 20.2g (0.1mol) diphenyl phosphate oxidation and 55g ethyl acetate are joined in reactor, and add 1ml tetrahydrofuran (THF) to cook phase-transfer catalyst, be warming up to again 60 ℃, then slowly add 12.2g (0.105mol) toxilic acid, keep 70 ℃ of temperature of reaction, react after 2 hours, filtration obtains white solid, obtain white powder by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice and be product, productive rate is 96%.
By 166g (1mol) pure terephthalic acid, 93g (1.5mol) ethylene glycol, 25.7g(9%wt) fire retardant DPO-MA puts in stainless steel cauldron together, passes into N
2be warming up to 230 ℃ and remain to esterification yield and reach 96%, then add 0.056g(0.02%wt) catalyst Ti acid butyl ester and 0.085g(0.03%wt) stablizer trimethyl phosphite 99, be warming up to again 270 ℃, in 45min, slowly decompression <10mmHg also keeps reaction 2h, obtains fire-resistant copolyesters ester composition.
Embodiment 13-16
The preparation method of embodiment 13-16 is as different from Example 12: in esterification process, the add-on of fire retardant DPO-MA is adjusted into 12%, 15%, 18%, 21%, and other are identical with embodiment 12.
Embodiment 17:
The preparation method of embodiment 17 is as different from Example 15: in slurry modulation process, the mol ratio of pure terephthalic acid and ethylene glycol is adjusted into 1.6, and other are identical with embodiment 15.
The contrast of above-described embodiment 12-17 performance is as shown in table 1:
The Performance Ratio of table 1 embodiment 12-17
In order to verify advantage of the present invention, the properties that table 1 has also been listed pure PET as a comparison.As can be seen from Table 1: compared with pure PET, not only have good flame retardant properties with the BACN DPO-MA flame retardant polyester composition of manufacture of the present invention, and mechanical property obtained good maintenance, the operability of carrying out downstream spinning is good; In the time of 1.75% left and right that phosphorus content is flame-proof copolyester, flame retardant rating reaches UL94V-0 level.
Claims (1)
1. one kind is utilized phosphorus flame retardant 1,2-dicarboxyl ethyl diphenyl phosphine oxide is prepared the method for halogen-free flame-retarded polyester composition, it is characterized in that, described phosphorus flame retardant 1,2-dicarboxyl ethyl diphenyl phosphine oxide is called for short DPO-MA, it carries out addition reaction acquisition take diphenyl phosphine oxide and toxilic acid as raw material, and reaction scheme is:
The detailed preparation method of DPO-MA is:
First pass into nitrogen excluding air to reactor, then in reactor, add diphenyl phosphate oxidation and solvent, and add a small amount of phase-transfer catalyst, be warming up to again 60 ℃, then slowly add toxilic acid, control temperature of reaction between 60-80 ℃, reaction is after 2-4 hour, filtration obtains white solid, obtains white powder be product by ice-cold benzene and tetrahydrofuran (THF) mixed solution washed twice;
Described solvent is one or more in benzene class, ester class, alkyl chloride hydro carbons; Solvent load is 1.5-3 times of diphenyl phosphine oxide quality;
Described diphenyl phosphine oxide and the mol ratio of toxilic acid are 1:(1-1.2);
Described phase-transfer catalyst is tetrahydrofuran (THF) or pyridine, and consumption is 3%～5% of diphenyl phosphine oxide quality;
Described benzene and tetrahydrofuran (THF) mixed solution are 2:1 preparation in mass ratio;
The method of utilizing DPO-MA to prepare halogen-free flame-retarded polyester composition is:
The first step: raw material is prepared
Take fire retardant DPO-MA, pure terephthalic acid TPA, ethylene glycol EG, catalyst Ti acid butyl ester and stablizer, wherein:
The adding proportion of described fire retardant DPO-MA is the 9%-21% of the each component gross weight of flame retardant polyester composition;
Described catalyzer adding proportion is 0～0.05% of the each component gross weight of flame retardant polyester composition;
Described stablizer is triphenyl phosphite or trimethyl phosphite 99; Stablizer adding proportion is 0～0.05% of the each component gross weight of flame retardant polyester composition;
Second step: the copolymerization of halogen-free flame-retarded polyester composition
Be (1.5～1.8) in molar ratio by EG and TPA: 1 adds in reactor, and adds fire retardant DPO-MA, passes into N in reactor
2be warming up to 230 ℃ and remain to esterification yield and reach 96%, then in reactor, add catalyzer and stablizer, then be warming up to 270 ℃, in 45min, be slowly decompressed to <10mmHg and keep reaction 2h to obtain halogen-free flame-retarded polyester composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310267672.4A CN103289124B (en) | 2013-06-28 | 2013-06-28 | Phosphorus flame retardant namely 1,2-dicarboxylic ethyl diphenyl phosphine oxide and preparation method thereof as well as halogen-free flame-retardant polyester composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310267672.4A CN103289124B (en) | 2013-06-28 | 2013-06-28 | Phosphorus flame retardant namely 1,2-dicarboxylic ethyl diphenyl phosphine oxide and preparation method thereof as well as halogen-free flame-retardant polyester composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103289124A CN103289124A (en) | 2013-09-11 |
| CN103289124B true CN103289124B (en) | 2014-07-02 |
Family
ID=49090693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310267672.4A Active CN103289124B (en) | 2013-06-28 | 2013-06-28 | Phosphorus flame retardant namely 1,2-dicarboxylic ethyl diphenyl phosphine oxide and preparation method thereof as well as halogen-free flame-retardant polyester composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103289124B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037715A (en) * | 2014-12-02 | 2015-11-11 | 淮安市欣佳尼龙有限公司 | Preparation method of flame-retarding nylon 610 and toothbrush hair produced therefrom |
| CN106633828B (en) * | 2017-01-06 | 2019-07-02 | 东华大学 | A kind of halogen-free flame-retardant polyamide 66 and preparation method thereof |
| CN106633043B (en) * | 2017-01-06 | 2019-06-25 | 东华大学 | A kind of halogen-free flame-retardant polyamide 6 and preparation method thereof |
| CN110156959B (en) * | 2019-05-13 | 2021-12-31 | 天津瑞远粉末涂料有限公司 | High-flame-retardance high-flexibility epoxy resin composition and preparation method thereof |
| CN110283359A (en) * | 2019-07-30 | 2019-09-27 | 中国科学技术大学 | A kind of N- phosphorus compound replaces phosphinimine type fire retardant and preparation method thereof |
| CN112442072A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Reactive flame retardant with carboxylic acid or anhydride group, and preparation method and application thereof |
| CN112442088A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with carboxyl and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508770A (en) * | 2009-03-17 | 2009-08-19 | 四川东材科技集团股份有限公司 | Method for preparing phosphor system halogen-free flame-proof copolymerization polyester |
| RU2405789C2 (en) * | 2008-07-17 | 2010-12-10 | Учреждение Российской Академии Наук Институт Физиологически Активных Веществ Ран (Ифав Ран) | Method for synthesis of phosphoryl-substituted 1,4-dicarboxylic acids |
-
2013
- 2013-06-28 CN CN201310267672.4A patent/CN103289124B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2405789C2 (en) * | 2008-07-17 | 2010-12-10 | Учреждение Российской Академии Наук Институт Физиологически Активных Веществ Ран (Ифав Ран) | Method for synthesis of phosphoryl-substituted 1,4-dicarboxylic acids |
| CN101508770A (en) * | 2009-03-17 | 2009-08-19 | 四川东材科技集团股份有限公司 | Method for preparing phosphor system halogen-free flame-proof copolymerization polyester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103289124A (en) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103289124B (en) | Phosphorus flame retardant namely 1,2-dicarboxylic ethyl diphenyl phosphine oxide and preparation method thereof as well as halogen-free flame-retardant polyester composition | |
| CN106243385B (en) | A kind of DOPO based flameproofings and preparation method thereof | |
| CN103102490B (en) | Phosphorus-containing polyol, its preparation method and comprise its flame retardant polyurethane | |
| CN102660010B (en) | Preparation method of reactive polyester flame-retardant additive | |
| CN103641859B (en) | Phosphor-containing flame-proof monomer and the halogen-free antiflaming polyester containing this monomer and preparation method thereof | |
| CN102702496B (en) | Preparation method of high-viscosity, wear-resistant, antistatic and flame-retardant polyester | |
| CN103333205A (en) | Phosphorus flame retardant 2,3-dicarboxylic propyl diphenyl phosphine oxide, preparation method and flame-retardant polyester composition thereof | |
| CN102585663B (en) | Halogen-free flame-retardant high-temperature-resistance insulation paint for motor | |
| CN103772740B (en) | Phosphonium flame retardant and preparation method thereof | |
| CN103102655A (en) | Inflaming retarding polyester film and preparation method thereof | |
| CN103554497A (en) | Method for preparing flame-retardant thermoplastic polyimide resin | |
| CN102660009B (en) | Preparation method of flame-retardant linear copolyester resin | |
| CN101407577A (en) | Low-melting point phosphor-containing flame-retardant copolyester and preparation thereof | |
| CN106397778A (en) | Method for increasing yield and polymerization degree of polymeric phosphorus-nitrogen intumescent flame retardant | |
| CN102400244A (en) | Method for producing flame-retardant melt-drip resistant polyester short fibers | |
| CN103242535A (en) | Linear water-soluble polyphosphazene high-molecular adhesive blended modified fire retardant | |
| CN104341596A (en) | DDM (4,4'-diaminodiphenylmethane) type active halogen-free flame retardant and preparation method thereof | |
| CN104341611B (en) | A kind of TGBD types organic fire-retardant and its preparation method and application | |
| CN106380485A (en) | DOPO-modified cyclophosphazene fire retardant and preparation and application thereof | |
| CN111763232B (en) | Phosphaphenanthrene/hypophosphite biradical flame retardant containing reactive groups and preparation method thereof | |
| CN103880611A (en) | Preparation method of bis(hydroxypropyl) bisphenol fluorene ether | |
| 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 | |
| CN102731575A (en) | Phosphorus bromine flame retardant agent and preparation method thereof | |
| CN112442072A (en) | Reactive flame retardant with carboxylic acid or anhydride group, and preparation method and application thereof | |
| CN109096493A (en) | A kind of polymerization reaction type Fire Retardant of The Expoxy Resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20130911 Assignee: Binhai Jinxiang Chemical Auxiliary Co., Ltd. Assignor: Shandong Univ. of Science & Technology Contract record no.: 2015320000609 Denomination of invention: Phosphorus flame retardant namely 1,2-dicarboxylic ethyl diphenyl phosphine oxide and preparation method thereof as well as halogen-free flame-retardant polyester composition Granted publication date: 20140702 License type: Exclusive License Record date: 20151013 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |