CN103360606A - Halogen-free organophosphate fire retardant and its preparation method - Google Patents
Halogen-free organophosphate fire retardant and its preparation method Download PDFInfo
- Publication number
- CN103360606A CN103360606A CN2013103096849A CN201310309684A CN103360606A CN 103360606 A CN103360606 A CN 103360606A CN 2013103096849 A CN2013103096849 A CN 2013103096849A CN 201310309684 A CN201310309684 A CN 201310309684A CN 103360606 A CN103360606 A CN 103360606A
- Authority
- CN
- China
- Prior art keywords
- halogen
- alcohol
- phenol
- proof agent
- ester flame
- 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
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a halogen-free organophosphate fire retardant and its preparation method. The fire retardant contains no halogen and will not release corrosive toxic gases when combusted. Through a reaction between polycarbonate polyol and isocyanate, an inflaming retarding element is embedded into a polyurethane foamed material and will not migrate or escape when the material is heated. Thus, the material is permanently endowed with flame resistance.
Description
Technical field
The present invention relates to a kind of halogen-free organophosphorous ester flame-proof agent and preparation method thereof, belong to the resistance combustion polyurethane foam field.
Background technology
Polyurethane foam is widely used in building thermal insulation material, furniture, seat cushions etc.Because it is inflammable, and polyurethane foam is carried out the flame-retardant modified focus that has become this area research.At present most widely used is halogenated flame retardant, but has easily migration, loss, and flame retardant resistance can not be lasting, produce the defectives such as more smog and poisonous gas (hydrogen halide) during burning, so halogenated flame retardant does not meet increasingly strict non-halogen requirement.By comparison, reactive phosphorus flame retardant has that consumption is low, do not discharge the characteristics such as corrosive gases when flame retardant resistance lasting stability and burning, is the flame-retardant modified better selection of polyurethane foam.
Chinese patent 201010227072.1 discloses a kind of preparation method of oligomerization phosphate polyalcohol, use has straight or branched monohydroxy-alcohol and the synthetic two chlorethoxyfos list alkane esters of phosphorus oxychloride of 1～4 carbon atom, aggregates into oligomerization phosphate polyalcohol with dibasic alcohol again.Because the product water dissolubility is large, need to remove byproduct hydrogen chloride with toxicity larger acid binding agent triethylamine and methylene dichloride, cause toxic substance residual.
Summary of the invention
The purpose of this invention is to provide the halogen-free organophosphorous ester flame-proof agent of a kind of response type, this fire retardant has overcome the deficiency on the above-mentioned phosphoric acid ester performance, and has solved the problem of introducing poisonous residue except byproduct hydrogen chloride.
Another object of the present invention provides a kind of method for preparing halogen-free organophosphorous ester flame-proof agent, and the application of this fire retardant on polyurethane foam.
For achieving the above object, the present invention adopts following technical scheme:
Described halogen-free organophosphorous ester flame-proof agent, its structural formula is as follows:
Wherein, R represents octyl group, iso-octyl, benzyl, phenyl ring; Polymerization degree n is 1～10 positive integer.
In the structural formula of described halogen-free organophosphorous ester flame-proof agent, the positive integer of polymerization degree n preferred 4～10.
The preparation method of described halogen-free organophosphorous ester flame-proof agent is as follows:
(1) monohydroxy-alcohol (phenol) and the mol ratio of phosphorus oxychloride according to 1:1, at first phosphorus oxychloride is placed reactor, stir the lower monohydroxy-alcohol (phenol) that slowly drips, time for adding is 1～3 hour, wait to dropwise, slowly heat up, keep 30～80 ℃ of reactions of temperature 1～2 hour, the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
(2) dibasic alcohol and phosphorus oxychloride are according to the mol ratio of 1.1～2:1, slowly splash into dibasic alcohol in the reactor again, time for adding is 0.25～0.75 hour, being warming up to 80～90 ℃ after dropwising continues to stir 1～3 hour, simultaneously the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
(3) the gained reaction solution is transferred to extraction kettle, 20～30 ℃ of control temperature, washing adds 1%～5% anhydrous sodium sulphate again and carries out drying, filtration until water dropping silver nitrate solution is not muddy repeatedly, obtains described hydroxyl fire retardant of polyphosphate.
The method of the halogen-free organophosphorous ester flame-proof agent of described preparation is characterized in that, monohydroxy-alcohol (phenol) described in the step (1) is any in phenol, phenylcarbinol, octanol, the isooctyl alcohol.
The method of the halogen-free organophosphorous ester flame-proof agent of described preparation is characterized in that, monohydroxy-alcohol (phenol) is phenylcarbinol or phenol described in the step (1).
The method of the halogen-free organophosphorous ester flame-proof agent of described preparation is characterized in that, dibasic alcohol described in the step (2) is any in ethylene glycol, 1,2-PD, the BDO.
The application of described halogen-free organophosphorous ester flame-proof agent in polyurethane hard foam, polyurethane foams.
Be described in further detail technical scheme of the present invention as follows:
The molecular structure of described halogen-free organophosphorous ester flame-proof agent is as follows:
Wherein, R is octyl group, iso-octyl, benzyl, phenyl ring;
Polymerization degree n is 1～10 positive integer, preferred 4～10 positive integer.
The preparation method of described halogen-free organophosphorous ester flame-proof agent is as follows:
(1) phosphorus oxychloride is placed reactor, stir the lower monohydroxy-alcohol (phenol) that slowly drips, wait to dropwise, slowly heat up, keep 30～80 ℃ of reactions of temperature 1～2 hour, the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases, wherein, temperature of reaction preferably is controlled at 40～50 ℃, more preferably 45～50 ℃, time for adding is 1～3 hour, be preferably 1～2 hour, obtain reaction solution, reaction formula is:
(2) slowly splash into dibasic alcohol in the reaction solution, be warming up to 80～90 ℃ after dropwising and continue to stir 1～3 hour, preferred 2 hours, simultaneously the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases, wherein, temperature of reaction preferably is controlled at 85～90 ℃, more preferably 90 ℃, time for adding is 0.25～0.75 hour, be preferably 0.5 hour, obtain mixture, reaction equation is:
(3) the gained reaction solution is transferred to extraction kettle, 20～30 ℃ of control temperature, preferred 30 ℃, washing is until water dropping silver nitrate solution is not muddy repeatedly, represent that then chlorion eliminates substantially in the product, add again 1%～5% anhydrous sodium sulphate and carry out drying, filtration, obtain described hydroxyl fire retardant of polyphosphate.
Described monohydroxy-alcohol (phenol) is any in octanol, isooctyl alcohol, phenylcarbinol, the phenol, preferred phenylcarbinol, phenol, and phenol more preferably, monohydroxy-alcohol (phenol) is 1:1 with the mol ratio of phosphorus oxychloride.
Described dibasic alcohol is any in ethylene glycol, 1,2-PD, the BDO, and the mol ratio of dibasic alcohol and phosphorus oxychloride is 1.1～2:1, preferred 1.1～1.5:1, more preferably 1.1:1.
The contriver finds that by great many of experiments when electing monohydroxy-alcohol (phenol) as octanol, isooctyl alcohol, phenylcarbinol, phenol (being that the R base is octyl group, iso-octyl, benzyl, phenyl ring), the hydrophobicity of poly phosphate of the present invention is stronger, and washing can be removed byproduct hydrogen chloride.When preparing polyurethane flexible foam and rigid foam with poly phosphate of the present invention, the flame retardant properties of this polyurethane foam meets national standard after testing.What in addition, exceed that the contriver expects is that the introducing of hydrophobic side chains (being the R side chain) has significantly improved the uniformity coefficient of polyurethane foam, does not add the foam that foam stabilizer also can make the abscess even compact during foaming.The R side chain is on the hydrophobicity of poly phosphate and as follows on the impact experiment of polyurethane foam uniformity coefficient:
Preparation method according to embodiment 1, only change the kind of monohydroxy-alcohol (phenol) in the step (1), the phenylcarbinol, octanol, isooctyl alcohol, propyl carbinol, methyl alcohol, ethanol, n-propyl alcohol, the isopropylcarbinol that namely add respectively 1 mole make the poly phosphate sample 1,2,3,4,5,6,7,8 of different R side chains.The method that washes with water is again removed byproduct hydrogen chloride, at last above-mentioned sample is made polyurethane foam (foaming formulation and reaction conditions are constant) through foaming, observes the uniformity coefficient of foam, and detected result is as shown in the table:
Table 1---R side chain is on the poly phosphate hydrophobicity and on the impact of foam uniformity coefficient
| ? | Monohydroxy-alcohol (phenol) | The phase-splitting degree * | The foam outward appearance |
| Embodiment 1 | Phenol | ++ | Foam is even, densification |
| Sample 1 | Phenylcarbinol | ++ | Foam is even, densification |
| Sample 2 | Octanol | + | Foam is even, densification |
| Sample 3 | Isooctyl alcohol | + | Foam is even, densification |
| Sample 4 | Propyl carbinol | + | Foam is inhomogeneous |
| Sample 5 | Methyl alcohol | - | ＼ |
| Sample 6 | Ethanol | - | ＼ |
| Sample 7 | Virahol | - | ＼ |
| Sample 8 | Isopropylcarbinol | - | ＼ |
Remarks: the phase-splitting degree represents very easily phase-splitting for " ++ ", and poly phosphate and water are fully incompatible; The phase-splitting of "+" expression energy has part poly phosphate and water miscible; "-" expression can not phase-splitting, and poly phosphate is water-soluble.Poly phosphate is after washing, if phase-splitting represents that then the hydrophobicity of this poly phosphate is good, washing is until aqueous phase dropping silver nitrate solution is not muddy repeatedly, and chlorion eliminates substantially in the expression product; If can not phase-splitting, represent that then this poly phosphate is water-soluble large, washing can't be removed byproduct hydrogen chloride.
The result shows in the table, when the R of poly phosphate side chain substituents is phenyl ring, benzyl, octyl group, iso-octyl, its hydrophobicity obviously is better than the alkyl poly phosphate that side chain is 1～4 carbon atom, can remove byproduct hydrogen chloride by washing, and greatly improve the uniformity coefficient of polyurethane foam.
Compared with prior art, characteristics of the present invention are:
1. in the process of preparation poly phosphate of the present invention, washing can be removed byproduct hydrogen chloride, has simplified aftertreatment technology,
Not only environmental protection but also reduce cost;
2. improve the uniformity coefficient of polyurethane foam, need not to add foam stabilizer;
3. flame retarding efficiency high and do not move, not loss, make material have lasting flame retardant properties;
4. in not halogen-containing, when burning, do not discharge the corrodibility toxic gas.
Embodiment
The present invention will be further described with specific embodiment for the below, but should not be construed as limiting the scope of the invention.
Embodiment 1: the preparation of organophosphate of the present invention
1. 153.5 gram (1 mole) phosphorus oxychloride are added in the reaction unit (mainly comprising reaction flask, whipping appts, Dropping feeder, heated for controlling temperature and gas absorbing device), drip again 94 gram phenol (1 mole) of in advance melting, about 1 hour of total time for adding, reacted 2 hours at 70～80 ℃ after dropwising, during this time the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
2. slowly add 68.2 gram ethylene glycol (1.1 moles) in the still, time for adding is 0.25 hour, the control temperature of charge continues reaction 2 hours between 80～90 ℃, during the absorption unit of water is equipped with in the hydrogenchloride introducing that generates, until concentration of hydrochloric acid no longer increases;
3. the gained reaction solution is transferred to separating funnel, 30 ℃ of control temperature, washing is until water is not muddy through 0.5 mol/L silver nitrate solution test solution repeatedly, adding 3% anhydrous sodium sulphate is dried to limpid again, get after filtration light yellow transparent liquid, be described hydroxyl fire retardant of polyphosphate.
After testing, phosphorus content is about 15%, and hydroxyl value is 51mgKOH/g, and the viscosity under 25 ℃ is 1080mPaS, and acid number is 0.5mgKOH/g.
Embodiment 2: the preparation of organophosphate of the present invention
1. 153.5 gram (1 mole) phosphorus oxychloride are added in the reaction unit (mainly comprising reaction flask, whipping appts, Dropping feeder, heated for controlling temperature and gas absorbing device), drip 108.1 gram phenylcarbinols (1 mole), total time for adding is 2 hours, reacted 1 hour at 30～40 ℃ after dropwising, the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
2. 68.2 gram ethylene glycol (1.1 moles) are slowly added in the still, time for adding is 0.5 hour, and the control temperature of charge continues reaction 2 hours between 80～90 ℃, during the absorption unit of water is equipped with in the hydrogenchloride introducing that generates, until concentration of hydrochloric acid no longer increases;
3. the gained reaction solution is transferred to extraction kettle, 30 ℃ of control temperature, washing adds 1% anhydrous sodium sulfate drying to limpid again until water is not muddy through 0.5 mol/L silver nitrate solution test solution repeatedly, get after filtration light yellow transparent liquid, be described hydroxyl fire retardant of polyphosphate.
After testing, phosphorus content is 14%, and hydroxyl value is 51mgKOH/g, and the viscosity under 25 ℃ is 950mPaS, and acid number is 0.4mgKOH/g.
Embodiment 3: the preparation of organophosphate of the present invention
1. first 153.5 gram (1 mole) phosphorus oxychloride are added in the reaction unit (mainly comprising reaction flask, whipping appts, Dropping feeder, heated for controlling temperature and gas absorbing device), drip 130.2 gram octanols (1 mole), total time for adding is 3 hours, reacted 1.5 hours at 30～40 ℃ after dropwising, during this time the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
2. then with 152.2 grams 1,2-propylene glycol (2 moles) slowly adds in the still, and time for adding is 0.75 hour, and the control temperature of charge continues reaction 1 hour between 80～90 ℃, during this time the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
3. again the gained reaction solution is transferred to separating funnel, 20 ℃ of control temperature, washing is until water is not muddy through 0.5 mol/L silver nitrate solution test solution repeatedly, add again 3% anhydrous sodium sulfate drying to limpid, get after filtration light yellow transparent liquid, be described hydroxyl fire retardant of polyphosphate.
After testing, phosphorus content is 10%, and hydroxyl value is 340mgKOH/g, and the viscosity under 25 ℃ is 700mPaS, and acid number is 0.5mgKOH/g.
Embodiment 4: the preparation of organophosphate of the present invention
1. first 153.5 gram (1 mole) phosphorus oxychloride are added in the reaction unit (mainly comprising reaction flask, whipping appts, Dropping feeder, heated for controlling temperature and gas absorbing device), drip 130.2 gram isooctyl alcohol (1 mole), total time for adding is 3 hours, reacted 1.5 hours at 30～40 ℃ after dropwising, during this time the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
2. then with 135 grams 1,4-butyleneglycol (1.5 moles) slowly adds in the still, and time for adding is 0.5 hour, and the control temperature of charge continues reaction 3 hours between 80～90 ℃, during this time the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
3. again the gained reaction solution is transferred to separating funnel, 25 ℃ of control temperature, washing is until water is not muddy through 0.5 mol/L silver nitrate solution test solution repeatedly, adding 5% anhydrous sodium sulphate is dried to limpid again, get after filtration light yellow transparent liquid, be described hydroxyl fire retardant of polyphosphate.
After testing, phosphorus content is 10%, and hydroxyl value is 370mgKOH/g, and the viscosity under 25 ℃ is 800mPaS, and acid number is 0.2mgKOH/g.
Embodiment 5: the halogen-free organophosphorous acid esters of the present invention is in the application of polyurethane flexible foam
Getting respectively the made hydroxyl poly phosphate and 100 of 15 gram embodiment 1 to 4 restrains polyether glycols (molecular mass is 3000g/mol, trifunctional, hydroxyl value is 56mgKOH/g) mix, use the TDI(tolylene diisocyanate) make solidifying agent, and add 0.4 the gram N, the N-dimethylethanolamine, the 0.2 gram stannous octoate experiment of foaming, the performance of after slaking, testing soft foam materials.The foaming envrionment temperature is 20 ± 1 ℃, and temperature of charge is 20 ± 0.5 ℃, 2500 rev/mins of stirring velocitys, churning time 5～10 seconds.Be " combustioncharacteristics of automotive interior material " according to GB8410-2006() the flame retardant properties of the made soft foam of standard test, the result is as shown in table 2:
Table 2 hydroxyl poly phosphate is in the application (according to GB8410-2006) of polyurethane foams
Embodiment 6: the halogen-free organophosphorous acid esters of the present invention is in the application of hard polyurethane foam
Getting respectively the made hydroxyl poly phosphate and 100 of 30 gram embodiment 1 to 4 restrains polyether glycols (molecular mass is 000g/mol, trifunctional, hydroxyl value is 56mgKOH/g) mix, with thick MDI(diphenylmethanediisocyanate) the solid agent of do, add again the 1.8g dimethyl cyclohexane, 1.2 gram DMP-30, the performance of stiff foam material is tested in 25 gram whipping agents (141b) experiments of foaming after ripe.The foaming envrionment temperature is 20 ± 1 ℃, and temperature of charge is 20 ± 0.5 ℃, 500 rev/mins of stirring velocitys, churning time 5-10 second.Be " material of construction and goods classification system for fire performance " according to GB8624-2006() standard check the flame retardant properties of made rigid foam, the result is as shown in table 3:
Table 3 hydroxyl poly phosphate is in the application (according to GB8624-2006) of polyurethane hard foam
The test result of embodiment 5 and embodiment 6 shows: after adding fire retardant of the present invention, the flame retardant properties of urethane plastic obviously improves, and all reaches good fire-retardant index.
Claims (7)
1. halogen-free organophosphorous ester flame-proof agent, structural formula is as follows:
Wherein, R represents octyl group, iso-octyl, benzyl, phenyl ring; Polymerization degree n is the positive integer between 1～10.
2. halogen-free organophosphorous ester flame-proof agent according to claim 1 is characterized in that, polymerization degree n is the positive integer between 4～10.
3. the preparation method of described halogen-free organophosphorous ester flame-proof agent according to claim 1 comprises the steps:
(1) monohydroxy-alcohol (phenol) and the mol ratio of phosphorus oxychloride according to 1:1, at first phosphorus oxychloride is placed reactor, stir the lower monohydroxy-alcohol (phenol) that slowly drips, time for adding is 1～3 hour, wait to dropwise, slowly heat up, keep 30～80 ℃ of reactions of temperature 1～2 hour, the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
(2) dibasic alcohol and phosphorus oxychloride are according to the mol ratio of 1.1～2:1, slowly splash into dibasic alcohol in the reactor again, time for adding is 0.25～0.75 hour, being warming up to 80～90 ℃ after dropwising continues to stir 1～3 hour, simultaneously the hydrogenchloride that generates is introduced the absorption unit that water is housed, until concentration of hydrochloric acid no longer increases;
(3) the gained reaction solution is transferred to extraction kettle, 20～30 ℃ of control temperature, washing adds 1%～5% anhydrous sodium sulphate again and carries out drying, filtration until water dropping silver nitrate solution is not muddy repeatedly, obtains described hydroxyl fire retardant of polyphosphate.
4. the method for the halogen-free organophosphorous ester flame-proof agent of described preparation according to claim 2 is characterized in that monohydroxy-alcohol (phenol) described in the step (1) is any in phenol, phenylcarbinol, octanol, the isooctyl alcohol.
5. the method for the halogen-free organophosphorous ester flame-proof agent of described preparation according to claim 2 is characterized in that monohydroxy-alcohol (phenol) is phenylcarbinol or phenol described in the step (1).
6. the method for the halogen-free organophosphorous ester flame-proof agent of described preparation according to claim 2 is characterized in that dibasic alcohol described in the step (2) is any in ethylene glycol, 1,2-PD, the BDO.
7. each described halogen-free organophosphorous ester flame-proof agent application in hard polyurethane foam, polyurethane flexible foam of claim 1～6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310309684.9A CN103360606B (en) | 2013-07-23 | 2013-07-23 | Halogen-free organophosphate fire retardant and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310309684.9A CN103360606B (en) | 2013-07-23 | 2013-07-23 | Halogen-free organophosphate fire retardant and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103360606A true CN103360606A (en) | 2013-10-23 |
| CN103360606B CN103360606B (en) | 2015-07-22 |
Family
ID=49362923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310309684.9A Active CN103360606B (en) | 2013-07-23 | 2013-07-23 | Halogen-free organophosphate fire retardant and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103360606B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497449A (en) * | 2014-12-23 | 2015-04-08 | 常熟市白茆通讯配件厂 | Guide vane wheel for dust collector |
| CN104672461A (en) * | 2013-11-26 | 2015-06-03 | 国际商业机器公司 | Flame retardant polymers containing renewable content and making method thereof |
| CN106397475A (en) * | 2016-08-18 | 2017-02-15 | 中国林业科学研究院林产化学工业研究所 | Vegetable oil-based polyol and its preparation method and use |
| CN106750174A (en) * | 2017-01-18 | 2017-05-31 | 西南交通大学 | A kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material and preparation method thereof |
| CN106977689A (en) * | 2017-04-20 | 2017-07-25 | 福建清源科技有限公司 | A kind of preparation method and application of aqueous polyurethane |
| CN107501509A (en) * | 2017-09-08 | 2017-12-22 | 湖北科技学院 | A kind of flexible polyurethane foam of phosphorus nitrogen cooperative flame retardant |
| CN107903440A (en) * | 2017-11-29 | 2018-04-13 | 云南云天化以化磷业研究技术有限公司 | A kind of Halogen alkyl phosphoric acid ester oligomer organic fire-retardant and preparation method thereof |
| CN108383973A (en) * | 2018-02-12 | 2018-08-10 | 吴艳飞 | A kind of full water foamed and sprayed soft flame retardant polyurethane thermal insulation material and preparation method thereof |
| CN109897219A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
| CN115353605A (en) * | 2022-09-15 | 2022-11-18 | 恩龙实业(嘉兴)有限公司 | In-situ flame-retardant polyurethane foam material and preparation method thereof |
| CN115873257A (en) * | 2021-09-29 | 2023-03-31 | 中国石油化工股份有限公司 | Halogenated polyphosphate polyol and polyurea elastomer, and preparation method and application thereof |
| CN116333286A (en) * | 2023-05-08 | 2023-06-27 | 广州光通科技有限公司 | Flame retardant with high phosphorus content and preparation method thereof |
| CN116694211A (en) * | 2023-05-31 | 2023-09-05 | 广州也乐新材料科技有限公司 | Preparation method and application of water-based two-component polyurethane flame-retardant material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5985965A (en) * | 1993-12-16 | 1999-11-16 | Clariant Gmbh | Flame-resistant polyurethanes |
| CN101899160A (en) * | 2010-07-15 | 2010-12-01 | 山东兄弟科技股份有限公司 | Preparation method of oligomerization phosphate polyalcohol |
| CN102558606A (en) * | 2012-01-11 | 2012-07-11 | 福州大学 | Reactive halogen-free organic phosphate ester flame retardant and flame-retardant polyurethane elastomer |
| CN102604111A (en) * | 2012-01-16 | 2012-07-25 | 苏州科技学院 | Novel preparation method of polymeric phosphate ester flame retardant containing active hydroxyl |
-
2013
- 2013-07-23 CN CN201310309684.9A patent/CN103360606B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5985965A (en) * | 1993-12-16 | 1999-11-16 | Clariant Gmbh | Flame-resistant polyurethanes |
| CN101899160A (en) * | 2010-07-15 | 2010-12-01 | 山东兄弟科技股份有限公司 | Preparation method of oligomerization phosphate polyalcohol |
| CN102558606A (en) * | 2012-01-11 | 2012-07-11 | 福州大学 | Reactive halogen-free organic phosphate ester flame retardant and flame-retardant polyurethane elastomer |
| CN102604111A (en) * | 2012-01-16 | 2012-07-25 | 苏州科技学院 | Novel preparation method of polymeric phosphate ester flame retardant containing active hydroxyl |
Non-Patent Citations (1)
| Title |
|---|
| 崔丽丽等: "有机磷阻燃剂的现状及发展前景", 《当代化工》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672461A (en) * | 2013-11-26 | 2015-06-03 | 国际商业机器公司 | Flame retardant polymers containing renewable content and making method thereof |
| CN104497449A (en) * | 2014-12-23 | 2015-04-08 | 常熟市白茆通讯配件厂 | Guide vane wheel for dust collector |
| CN106397475A (en) * | 2016-08-18 | 2017-02-15 | 中国林业科学研究院林产化学工业研究所 | Vegetable oil-based polyol and its preparation method and use |
| CN106397475B (en) * | 2016-08-18 | 2018-06-26 | 中国林业科学研究院林产化学工业研究所 | A kind of vegetable oil-based polyols and its preparation method and application |
| CN106750174A (en) * | 2017-01-18 | 2017-05-31 | 西南交通大学 | A kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material and preparation method thereof |
| CN106750174B (en) * | 2017-01-18 | 2019-08-20 | 西南交通大学 | A kind of fire-retardant phase-change energy-storing heat preservation heat-barrier material and preparation method thereof |
| CN106977689B (en) * | 2017-04-20 | 2019-09-13 | 福建清源科技有限公司 | A kind of preparation method and application of aqueous polyurethane |
| CN106977689A (en) * | 2017-04-20 | 2017-07-25 | 福建清源科技有限公司 | A kind of preparation method and application of aqueous polyurethane |
| CN107501509A (en) * | 2017-09-08 | 2017-12-22 | 湖北科技学院 | A kind of flexible polyurethane foam of phosphorus nitrogen cooperative flame retardant |
| CN107903440A (en) * | 2017-11-29 | 2018-04-13 | 云南云天化以化磷业研究技术有限公司 | A kind of Halogen alkyl phosphoric acid ester oligomer organic fire-retardant and preparation method thereof |
| CN109897219A (en) * | 2017-12-11 | 2019-06-18 | 广东广山新材料股份有限公司 | A kind of reactive flame retardant and its preparation method and application |
| CN108383973A (en) * | 2018-02-12 | 2018-08-10 | 吴艳飞 | A kind of full water foamed and sprayed soft flame retardant polyurethane thermal insulation material and preparation method thereof |
| CN108383973B (en) * | 2018-02-12 | 2020-12-22 | 吴艳飞 | Full-water foaming spraying soft flame-retardant polyurethane thermal insulation material and preparation method thereof |
| CN115873257A (en) * | 2021-09-29 | 2023-03-31 | 中国石油化工股份有限公司 | Halogenated polyphosphate polyol and polyurea elastomer, and preparation method and application thereof |
| CN115873257B (en) * | 2021-09-29 | 2024-04-09 | 中国石油化工股份有限公司 | Halogenated polyphosphate polyol and polyurea elastomer, and preparation methods and applications thereof |
| CN115353605A (en) * | 2022-09-15 | 2022-11-18 | 恩龙实业(嘉兴)有限公司 | In-situ flame-retardant polyurethane foam material and preparation method thereof |
| CN116333286A (en) * | 2023-05-08 | 2023-06-27 | 广州光通科技有限公司 | Flame retardant with high phosphorus content and preparation method thereof |
| CN116694211A (en) * | 2023-05-31 | 2023-09-05 | 广州也乐新材料科技有限公司 | Preparation method and application of water-based two-component polyurethane flame-retardant material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103360606B (en) | 2015-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103360606A (en) | Halogen-free organophosphate fire retardant and its preparation method | |
| CN101899160B (en) | Preparation method of oligomerization phosphate polyalcohol | |
| CA2844567C (en) | Novel phosphonamidates - synthesis and flame retardant applications | |
| CN101381444B (en) | Environment friendly non-halogen reacting phosphorus-nitrogen coordinated fire-retardant aqueous polyurethane and preparation method thereof | |
| CN103360567B (en) | A kind of flame-retardant flexible polyurethane foam plastics | |
| ES2714250T3 (en) | Use of trialkyl phosphate as a smoke suppressor in polyurethane foam | |
| CN106432740B (en) | Hydroxyl-containing polyphosphonate flame retardant and preparation method and application thereof | |
| CN103694434A (en) | Halogen-free reaction type flame retardant for polyurethane foam as well as preparation method and application thereof | |
| CN105542101B (en) | Hard polyurethane foams Compositional type expanding fire retardant | |
| CN107892739B (en) | A kind of flame retarded rigid polyurethane foams plastics and preparation method thereof | |
| US3247134A (en) | Fire retardant cellular polyurethane compositions containing an organic phosphate amine salt | |
| CN112250858B (en) | Method for preparing flame-retardant polymer polyol, application and polyurethane foam plastic prepared by using flame-retardant polymer polyol | |
| CN103360566B (en) | A kind of flame retarded rigid polyurethane foams plastics | |
| JPS6245609A (en) | Production of fire retardant flexible polyurethane foam stabilized against burning and discoloration | |
| CN102585135A (en) | Reactive intumescent flame retardant for polyurethane and synthesis method of reactive intumescent flame retardant | |
| CN105085575A (en) | Flame-retardant polyol containing phosphorus linked pendant groups and preparation method of polyol | |
| CN104892886A (en) | Hard flame-retardant polyurethane foam low in smoke release | |
| CN104892889B (en) | A kind of hard resistance combustion polyurethane foam | |
| CN110862505A (en) | Polyisocyanurate foam and preparation method thereof | |
| CN103974990A (en) | Sugar-based polyurethanes, methods for their preparation, and methods of use thereof | |
| KR102455819B1 (en) | low viscosity phosphate polyols | |
| CN105669931A (en) | Halogen-free polyurethane foam material with low smoke density and high flame retardance and preparation method of halogen-free polyurethane foam material | |
| EP1171545B1 (en) | Flame retardant blend containing monomeric and oligomeric flame retardants | |
| US3956200A (en) | Flame retardant blends for flexible polyurethane foams | |
| CN111518251A (en) | Polyurethane rigid foam 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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220105 Address after: 215500 No. 22, Dongzhou Road, Changshu Economic Development Zone, Suzhou, Jiangsu Patentee after: CHANGSHU GUOHE NEW MATERIAL CO.,LTD. Address before: No. 456, Nansan Road, Chengdu Economic and Technological Development Zone, Chengdu, Sichuan 610065 Patentee before: SICHUAN GUOHE NEW MATERIALS Co.,Ltd. |
|
| TR01 | Transfer of patent right |