CN107141467A - The preparation method of phosphorus chlorine composite flame-proof polyethers - Google Patents
The preparation method of phosphorus chlorine composite flame-proof polyethers Download PDFInfo
- Publication number
- CN107141467A CN107141467A CN201710507383.5A CN201710507383A CN107141467A CN 107141467 A CN107141467 A CN 107141467A CN 201710507383 A CN201710507383 A CN 201710507383A CN 107141467 A CN107141467 A CN 107141467A
- Authority
- CN
- China
- Prior art keywords
- proof
- composite flame
- phosphorus
- preparation
- polyethers
- 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.)
- Pending
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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
- C08G18/5078—Polyethers having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
-
- 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 invention belongs to technical field of chemical synthesis, and in particular to a kind of preparation method of phosphorus chlorine composite flame-proof polyethers.Aqueous slkali is added in trihydroxy methyl phosphorous oxide and condensing agent, pH is adjusted, obtains phosphorus element-containing initiator；Phosphorus element-containing initiator is reacted with oxyalkylene, aging after reaction, obtains phosphorous PPG；Phosphate and chlorinated paraffin are added in phosphorous PPG, chlorine phosphorus composite flame-proof polyethers is obtained.Present invention process is simple, and reaction time is short, and favorable reproducibility, equipment requirement is low；Prepared flame retarding polyether viscosity and activity are adjustable, and stability is good；Polyurethane foam oxygen index (OI) prepared by flame retarding polyether is high, flame retardant effect persistently and foam size stability is good, disclosure satisfy that the demand of different clients.
Description
Technical field
The invention belongs to technical field of chemical synthesis, and in particular to a kind of preparation method of phosphorus chlorine composite flame-proof polyethers.
Background technology
RPUF has good intensity and powerful insulation and sound insulation value, in building field by not
Disconnected popularization and use, but polyurethane material belongs to flammable macromolecule, the potential safety hazard that there is burning and blast, has resulted in number
Fire is played, therefore, exploitation flame retarded polyurethane-foam turns into the requirement of market and society.In recent years, China develops very in succession
Many BACNs, are broadly divided into additive flame retardant and reactive flame retardant.Additive flame retardant is by mechanical mixture side
Fire retardant is added in polymer by method, polymer is had anti-flammability, and current additive flame retardant mainly has organic fire-retardant
And inorganic combustion inhibitor, halogenated flame retardant and non-halogen fire retardant.Physical and mechanical properties influence of the additive flame retardant on product is smaller,
But application surface is narrow, less varieties, and price is higher.Reactive flame retardant refers to add during macromolecular polymerization reaction fire-retardant anti-
System is answered, is identified oneself with monomeric form in reaction, by being chemically bonded the part as polymer.Therefore polymer is made in itself
Containing flame-retardant composition, smaller is influenceed on polymeric material performance, anti-flammability is lasting.
The content of the invention
It is an object of the invention to provide a kind of preparation method of phosphorus chlorine composite flame-proof polyethers, this method process stabilizing is kept
The viscosity and reactivity of flame retardant polyether polyol can be adjusted in the case that hydroxyl value and degree of functionality are stable by adding complexing agent, and
The fire resistance of prepared flame retardant polyether polyol is high, good with combining material system intersolubility.
The preparation method of phosphorus chlorine composite flame-proof polyethers of the present invention, step is as follows：
(1) aqueous slkali is added in trihydroxy methyl phosphorous oxide and condensing agent, adjusts pH, obtain phosphorus element-containing initiator；
(2) phosphorus element-containing initiator is reacted with oxyalkylene, aging after reaction, obtains phosphorous PPG；
(3) phosphate and chlorinated paraffin are added in phosphorous PPG, chlorine phosphorus composite flame-proof polyethers is obtained.
The mass ratio of trihydroxy methyl phosphorous oxide and condensing agent described in step (1) is 100：1-10.
Condensing agent described in step (1) is formalin or paraformaldehyde.
Aqueous slkali described in step (1) is potassium hydroxide solution or sodium hydroxide solution, the addition of aqueous slkali be containing
The 0.1-0.6% of phosphorus PPG quality.
PH described in step (1) is 8-12.
Oxyalkylene described in step (2) is in expoxy propane, oxirane, epoxychloropropane or epoxy chloroethanes
It is one or more of.
The mass ratio of oxyalkylene and trihydroxy methyl phosphorous oxide described in step (2) is 100-400：100.
Reaction condition described in step (2) is 100-120 DEG C of oxygen-free atmosphere, and reaction pressure is 0.1-0.4MPa, instead
It is 5-8h between seasonable.
Ageing time described in step (2) is 1-3h.
Phosphate described in step (3) is tricresyl phosphate (2- chloropropyls) ester, three (2- carboxyethyls) phosphines, tricresyl phosphate (1,3-
Two chloropropyls) one or more in ester or dimethyl methyl phosphonate.
The mass ratio of phosphorous PPG and phosphate described in step (3) is 100:10-20, phosphorous polyether polyols
The mass ratio of alcohol and chlorinated paraffin is 100:10-20.
The preparation method of phosphorus chlorine composite flame-proof polyethers of the present invention, is comprised the following steps that：
(1) trihydroxy methyl phosphorous oxide liquid and condensing agent in mass ratio 100:1-10 adds aqueous slkali after being mixed evenly
Regulation pH is 8-12, and the preferred formalin of condensing agent, reaction environment removing oxygen is protected with nitrogen, is gradually heating to 100-
110 DEG C, oxyalkylene reaction is slowly added to, charging finishes rear aging 1-3h, trihydroxy methyl phosphorous oxide and oxyalkylene quality
Than for 100:100-400.
(2) obtain phosphorous PPG after trihydroxy methyl phosphorous oxide, formaldehyde and oxyalkylene reaction, add phosphate and
Chlorinated paraffin, on the one hand can introduce fire-retardant chlorine element, obtain composite flame-proof polyethers, on the other hand can reduce system viscosity, stirring
The unnecessary water of heating removing after uniform.
The present invention compared with prior art, has the advantages that：
Present invention process is simple, and reaction time is short, and favorable reproducibility, equipment requirement is low；Prepared flame retarding polyether viscosity and
Activity is adjustable, and stability is good；Polyurethane foam oxygen index (OI) prepared by flame retarding polyether is high, flame retardant effect is lasting and foam size is steady
It is qualitative good, it disclosure satisfy that the demand of different clients.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2.5L autoclaves of sensor, trihydroxy methyl phosphorous oxide 300g, paraformaldehyde 3g and 48.3%KOH aqueous solution 6.52g are added,
80 DEG C are warming up to, expoxy propane 300g is gradually added, keeps pressure to be less than 0.4MPa, 110 DEG C of temperature is maintained.Treat that expoxy propane adds
Material finishes rear aging 2h, and nitrogen is mended 1 time in centre.Aging is vacuumized after finishing removes unreacted expoxy propane, and holding vacuum-
Phosphorous PPG is obtained after 0.08MPa, nitrogen bubble 1h.95g tricresyl phosphates (2- chloropropyls) ester and 95g are added into system
Chlorinated paraffin, is vacuumized after stirring 1h is well mixed, and unnecessary moisture in removing system keeps vacuum -0.08MPa, temperature
105 DEG C, phosphorus chlorine composite flame-proof polyethers is obtained after nitrogen bubble 2h.
Synthesized phosphorus chlorine composite flame-proof polyethers has following property：
Hydroxyl value：600mgKOH/g
26 DEG C of viscosity：11500mPas
Its moisture is：0.06%
Outward appearance：Light yellow clear
Activity：Reactivity is high
Embodiment 2
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2.5L autoclaves of sensor, trihydroxy methyl phosphorous oxide 300g, paraformaldehyde 3g and 48.3%KOH aqueous solution 6.52g are added,
80 DEG C are warming up to, expoxy propane 600g is gradually added, keeps pressure to be less than 0.4MPa, 110 DEG C of temperature is maintained.Treat that expoxy propane adds
Material finishes rear aging 2h, and nitrogen is mended 1 time in centre.Aging is vacuumized after finishing removes unreacted expoxy propane, and holding vacuum-
Phosphorous PPG is obtained after 0.08MPa, nitrogen bubble 1h.(2- carboxyethyls) phosphines of 95g tri- and 95g chlorine are added into system
Fossil waxes, are vacuumized after stirring 1h is well mixed, and unnecessary moisture in removing system keeps vacuum -0.08MPa, temperature
105 DEG C, phosphorus chlorine composite flame-proof polyethers is obtained after nitrogen bubble 2h.
Synthesized phosphorus chlorine composite flame-proof polyethers has following property：
Hydroxyl value：400mgKOH/g
26 DEG C of viscosity：7700mPas
Its moisture is：0.05%
Outward appearance：Light yellow clear
Activity：Reactivity is high
Embodiment 3
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2.5L autoclaves of sensor, trihydroxy methyl phosphorous oxide 300g, paraformaldehyde 3g and 48.3%KOH aqueous solution 6.52g are added,
80 DEG C are warming up to, expoxy propane 756g is gradually added, keeps pressure to be less than 0.4MPa, 110 DEG C of temperature is maintained.Treat that expoxy propane adds
Material finishes rear aging 2h, and nitrogen is mended 1 time in centre.Aging is vacuumized after finishing removes unreacted expoxy propane, and holding vacuum-
Phosphorous PPG is obtained after 0.08MPa, nitrogen bubble 1h.95g tricresyl phosphates (chloropropyls of 1,3- bis-) ester is added into system
With 95g chlorinated paraffins, vacuumized after stirring 1h is well mixed, unnecessary moisture in removing system keeps vacuum -0.08MPa,
Phosphorus chlorine composite flame-proof polyethers is obtained after 105 DEG C of temperature, nitrogen bubble 2h.
Synthesized phosphorus chlorine composite flame-proof polyethers has following property：
Hydroxyl value：350mgKOH/g
26 DEG C of viscosity：6500mPas
Its moisture is：0.04%
Outward appearance：Light yellow clear
Activity：Reactivity is high
Embodiment 4
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2.5L autoclaves of sensor, trihydroxy methyl phosphorous oxide 300g, formalin 8g and the 48.3%KOH aqueous solution are added
6.52g, is warming up to 80 DEG C, gradually adds expoxy propane 965g, keeps pressure to be less than 0.4MPa, maintains 110 DEG C of temperature.Treat epoxy
Propane charging finishes rear aging 2h, and nitrogen is mended 1 time in centre.Aging vacuumizes the unreacted expoxy propane of removing after finishing, keep
Phosphorous PPG is obtained after vacuum -0.08MPa, nitrogen bubble 1h.95g tricresyl phosphates (2- chloropropyls) are added into system
Ester and 95g chlorinated paraffins, are vacuumized, unnecessary moisture in removing system after stirring 1h is well mixed, and holding vacuum-
Phosphorus chlorine composite flame-proof polyethers is obtained after 0.08MPa, 105 DEG C of temperature, nitrogen bubble 2h.
Synthesized phosphorus chlorine composite flame-proof polyethers has following property：
Hydroxyl value：300mgKOH/g
26 DEG C of viscosity：5500mPas
Its moisture is：0.07%
Outward appearance：Light yellow clear
Activity：Reactivity is high
Embodiment 5
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2.5L autoclaves of sensor, trihydroxy methyl phosphorous oxide 300g, formalin 8g and the 48.3%KOH aqueous solution are added
6.52g, is warming up to 80 DEG C, gradually adds expoxy propane 1200g, keeps pressure to be less than 0.4MPa, maintains 110 DEG C of temperature.Treat ring
Ethylene Oxide charging finishes rear aging 2h, and nitrogen is mended 1 time in centre.Aging vacuumizes the unreacted expoxy propane of removing after finishing, protect
Phosphorous PPG is obtained after holding vacuum -0.08MPa, nitrogen bubble 1h.160g methylphosphonic acid diformazans are added into system
Ester and 160g chlorinated paraffins, are vacuumized, unnecessary moisture in removing system after stirring 1h is well mixed, and holding vacuum-
Phosphorus chlorine composite flame-proof polyethers is obtained after 0.08MPa, 105 DEG C of temperature, nitrogen bubble 2h.
Synthesized phosphorus chlorine composite flame-proof polyethers has following property：
Hydroxyl value：240mgKOH/g
26 DEG C of viscosity：4000mPas
Its moisture is：0.05%
Outward appearance：Light yellow clear
Activity：Reactivity is high
Embodiment 6
It is being equipped with agitator, meter, heating temperature control device, cooling device (including external jacket and inner coil pipe) and pressure
In the 2.5L autoclaves of sensor, trihydroxy methyl phosphorous oxide 300g, formalin 8g and the 48.3%KOH aqueous solution are added
6.52g, is warming up to 80 DEG C, gradually adds expoxy propane 548g, keeps pressure to be less than 0.4MPa, maintains 110 DEG C of temperature.Treat epoxy
Propane charging finishes rear aging 2h, and nitrogen is mended 1 time in centre.Aging vacuumizes the unreacted expoxy propane of removing after finishing, keep
Phosphorous PPG is obtained after vacuum -0.08MPa, nitrogen bubble 1h.95g tricresyl phosphates (2- chloropropyls) are added into system
Ester and 95g chlorinated paraffins, are vacuumized, unnecessary moisture in removing system after stirring 1h is well mixed, and holding vacuum-
Phosphorus chlorine composite flame-proof polyethers is obtained after 0.08MPa, 105 DEG C of temperature, nitrogen bubble 2h.
Synthesized phosphorus chlorine composite flame-proof polyethers has following property：
Hydroxyl value：420mgKOH/g
26 DEG C of viscosity：8200mPas
Its moisture is：0.07%
Outward appearance：Light yellow clear
Activity：Reactivity is high.
Claims (10)
1. a kind of preparation method of phosphorus chlorine composite flame-proof polyethers, it is characterised in that step is as follows：
(1) aqueous slkali is added in trihydroxy methyl phosphorous oxide and condensing agent, adjusts pH, obtain phosphorus element-containing initiator；
(2) phosphorus element-containing initiator is reacted with oxyalkylene, aging after reaction, obtains phosphorous PPG；
(3) phosphate and chlorinated paraffin are added in phosphorous PPG, chlorine phosphorus composite flame-proof polyethers is obtained.
2. the preparation method of phosphorus chlorine composite flame-proof polyethers according to claim 1, it is characterised in that described in step (1)
The mass ratio of trihydroxy methyl phosphorous oxide and condensing agent is 100：1-10.
3. the preparation method of phosphorus chlorine composite flame-proof polyethers according to claim 1, it is characterised in that described in step (1)
Condensing agent is formalin or paraformaldehyde.
4. the preparation method of phosphorus chlorine composite flame-proof polyethers according to claim 1, it is characterised in that described in step (1)
Aqueous slkali is potassium hydroxide solution or sodium hydroxide solution, and the addition of aqueous slkali is the 0.1- of phosphorous PPG quality
0.6%.
5. the preparation method of phosphorus chlorine composite flame-proof polyethers according to claim 1, it is characterised in that described in step (2)
Oxyalkylene is the one or more in expoxy propane, oxirane, epoxychloropropane or epoxy chloroethanes.
6. the preparation method of phosphorus chlorine composite flame-proof polyethers according to claim 1, it is characterised in that described in step (2)
Oxyalkylene and the mass ratio of trihydroxy methyl phosphorous oxide are 100-400：100.
7. the preparation method of phosphorus chlorine composite flame-proof polyethers according to claim 1, it is characterised in that described in step (2)
Reaction condition is 100-120 DEG C of oxygen-free atmosphere, and reaction pressure is 0.1-0.4MPa, and the reaction time is 5-8h.
8. the preparation method of phosphorus chlorine composite flame-proof polyethers according to claim 1, it is characterised in that described in step (2)
Ageing time is 1-3h.
9. the preparation method of phosphorus chlorine composite flame-proof polyethers according to claim 1, it is characterised in that described in step (3)
Phosphate is tricresyl phosphate (2- chloropropyls) ester, three (2- carboxyethyls) phosphines, tricresyl phosphate (chloropropyls of 1,3- bis-) ester or methylphosphonic acid two
One or more in methyl esters.
10. the preparation method of phosphorus chlorine composite flame-proof polyethers according to claim 1, it is characterised in that described in step (3)
Phosphorous PPG and phosphate mass ratio be 100:10-20, the mass ratio of phosphorous PPG and chlorinated paraffin
For 100:10-20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710507383.5A CN107141467A (en) | 2017-06-28 | 2017-06-28 | The preparation method of phosphorus chlorine composite flame-proof polyethers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710507383.5A CN107141467A (en) | 2017-06-28 | 2017-06-28 | The preparation method of phosphorus chlorine composite flame-proof polyethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107141467A true CN107141467A (en) | 2017-09-08 |
Family
ID=59786123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710507383.5A Pending CN107141467A (en) | 2017-06-28 | 2017-06-28 | The preparation method of phosphorus chlorine composite flame-proof polyethers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107141467A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903388A (en) * | 2017-11-28 | 2018-04-13 | 山东诺威新材料有限公司 | Rigid-foam polyether polyol and preparation method for mining grout material |
| CN109400866A (en) * | 2018-09-29 | 2019-03-01 | 山东诺威新材料有限公司 | Flame retardant type sponge polyether polyol and preparation method thereof |
| CN112646165A (en) * | 2020-12-14 | 2021-04-13 | 山东一诺威新材料有限公司 | Preparation method and application of halogen-free flame-retardant polyether polyol |
| CN114230752A (en) * | 2021-11-30 | 2022-03-25 | 山东一诺威新材料有限公司 | Intrinsic flame-retardant self-repairing polyurethane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747371A (en) * | 2009-12-09 | 2010-06-23 | 湖北福瑞斯化工科技有限公司 | Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and preparation method thereof |
| CN103626951A (en) * | 2012-08-21 | 2014-03-12 | 山东固安特新材料科技股份有限公司 | Special engineering material for reinforcement and preparing method therefor |
| CN105801833A (en) * | 2016-03-25 | 2016-07-27 | 江阴职业技术学院 | Preparation method and application of reactive type halogen-free flame-retardant polyether glycol |
| CN106750248A (en) * | 2017-01-24 | 2017-05-31 | 中国科学技术大学 | A kind of hyperbranched flame retardant polyether polyol and preparation method thereof |
-
2017
- 2017-06-28 CN CN201710507383.5A patent/CN107141467A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747371A (en) * | 2009-12-09 | 2010-06-23 | 湖北福瑞斯化工科技有限公司 | Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and preparation method thereof |
| CN103626951A (en) * | 2012-08-21 | 2014-03-12 | 山东固安特新材料科技股份有限公司 | Special engineering material for reinforcement and preparing method therefor |
| CN105801833A (en) * | 2016-03-25 | 2016-07-27 | 江阴职业技术学院 | Preparation method and application of reactive type halogen-free flame-retardant polyether glycol |
| CN106750248A (en) * | 2017-01-24 | 2017-05-31 | 中国科学技术大学 | A kind of hyperbranched flame retardant polyether polyol and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903388A (en) * | 2017-11-28 | 2018-04-13 | 山东诺威新材料有限公司 | Rigid-foam polyether polyol and preparation method for mining grout material |
| CN109400866A (en) * | 2018-09-29 | 2019-03-01 | 山东诺威新材料有限公司 | Flame retardant type sponge polyether polyol and preparation method thereof |
| CN112646165A (en) * | 2020-12-14 | 2021-04-13 | 山东一诺威新材料有限公司 | Preparation method and application of halogen-free flame-retardant polyether polyol |
| CN112646165B (en) * | 2020-12-14 | 2022-12-09 | 山东一诺威新材料有限公司 | Preparation method and application of halogen-free flame-retardant polyether polyol |
| CN114230752A (en) * | 2021-11-30 | 2022-03-25 | 山东一诺威新材料有限公司 | Intrinsic flame-retardant self-repairing polyurethane and preparation method thereof |
| CN114230752B (en) * | 2021-11-30 | 2023-07-18 | 山东一诺威新材料有限公司 | Intrinsic flame-retardant self-repairing polyurethane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107141467A (en) | The preparation method of phosphorus chlorine composite flame-proof polyethers | |
| CN104844781B (en) | A kind of graphene chemical modification hard polyurethane foams | |
| CN105131580B (en) | A kind of soft bubble of halogen-free anti-inflaming polyurethane and preparation method thereof | |
| CN106750112B (en) | A kind of highly effective flame-retardant slow rebound polyurethane sponge and preparation method thereof | |
| CN102276837B (en) | Halogen-free phosphorus-containing flame retardant polyimide resin composite and preparation method thereof | |
| CN105585707B (en) | A kind of synthetic method of flame-retardant rigid-foam polyether polyol | |
| Lin et al. | Study on thermal degradation and combustion behavior of flame retardant unsaturated polyester resin modified with a reactive phosphorus containing monomer | |
| CN104311877B (en) | A kind of response type nylon fire retardant and preparation method | |
| CN104177695A (en) | Crosslinked halogen-free flame-retardant cable material | |
| CN105199096A (en) | Preparation and application of nitrogen and phosphorus structured flame-retardant polyether polyol | |
| TW201107415A (en) | Thermoplastic/composition with epoxidized novolac | |
| CN104945597B (en) | A kind of build crosslinking with fire resistance can repair the synthetic method of polyurethane | |
| CN107573479A (en) | Utilize the preparation method of the intrinsic modified aqueous polyurethane of phosphorus flame retardant | |
| Shao et al. | Aqueous-based polyurethane with dual-functional curing agent | |
| CN104031544B (en) | A kind of preparation method of flame-retardant aqueous polyurethane coating | |
| CN105713167A (en) | High-flame-retardant rigid polyurethane foamed plastic and preparation method thereof | |
| CN108912169B (en) | Compound di- (4-aminophenyl) phenylphosphonate and synthesis method thereof | |
| CN106496549A (en) | A kind of organophosphor system fire-resistant copolyesters nylon and preparation method thereof | |
| Deng et al. | Synthesis and effect of hyperbranched (3-hydroxyphenyl) phosphate as a curing agent on the thermal and combustion behaviours of novolac epoxy resin | |
| CN107955155B (en) | Nitrogen-boron structure type flame-retardant polyether polyol and preparation method and application thereof | |
| CN113801162B (en) | Diacid monomer, copolymerized flame retardant, copolymerized flame-retardant nylon and preparation method thereof | |
| CN104745051A (en) | Preparation method of intumescent fire retardant paint based on unsaturated polyester resin | |
| Wang et al. | Synthesis of polyols containing nitrogen‐phosphorus from vegetable oil derivatives for polyurethane film applications | |
| CN112250705A (en) | Reactive oligomeric phosphate flame retardant and preparation method and application thereof | |
| CN107501856B (en) | Preparation method of flame-retardant modified wood fiber composite phenolic foam |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170908 |