CN109400866A - Flame retardant type sponge polyether polyol and preparation method thereof - Google Patents
Flame retardant type sponge polyether polyol and preparation method thereof Download PDFInfo
- Publication number
- CN109400866A CN109400866A CN201811148261.2A CN201811148261A CN109400866A CN 109400866 A CN109400866 A CN 109400866A CN 201811148261 A CN201811148261 A CN 201811148261A CN 109400866 A CN109400866 A CN 109400866A
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- Prior art keywords
- flame retardant
- polyether polyol
- retardant type
- type sponge
- oxide
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- 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
- C08G18/509—Polyethers having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
-
- 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
- C08G65/2618—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 nitrogen
- C08G65/2621—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 nitrogen containing amine groups
- C08G65/263—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 nitrogen containing amine groups containing heterocyclic amine groups
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
The present invention relates to a kind of flame retardant type sponge polyether polyol and preparation method thereof, belong to polyether polyol synthesis technical field.Flame retardant type sponge polyether polyol of the present invention, it is with polyester 1000 and trihydroxy methyl phosphorous oxide (THPO) for initiator, flame retardant type sponge polyether polyol is made with propylene oxide and epoxyethane ring-expansion polymerization using modified bimetallic cyanide complex catalyst.Flame retardant type sponge polyether polyol of the present invention, raw material is simple and easy to get, at low cost, stable structure, and anti-flammability is good；Invention also provides scientific and reasonable, simple and easy preparation methods.
Description
Technical field
The present invention relates to a kind of flame retardant type sponge polyether polyol and preparation method thereof, belong to polyether polyol synthesis skill
Art field.
Background technique
The referred to as soft bubble of polyurethane soft foamed plastics, is commonly called as sponge, refers to the flexibility polyurethane foam with certain elasticity
Foam plastics are mainly used for furniture mat material, vehicle seat cushion material and various soft liner laminar composites, application range
Widely.
Sponge has very strong flammability as a kind of porous organic polymer, there is very big security risk, tradition
The method of raising sponge flame retardant property be the fire-retardant mixing adding halogen containing polymers or halogen containing flame-retardant in formula and being composed
Object.For this method there are many problems, the fire retardant of addition can reduce the mechanical performance of sponge product；As time went on, it hinders
Combustion agent is likely to occur migration and is precipitated from product, influences stability and anti-flammability；Halogen-containing fire retardant is in product burns
When can discharge smog and toxic gas.
The method that another kind improves anti-flammability is that ignition-proof element and group are introduced in molecular structure, but existing method or resistance
Fuel efficiency fruit is undesirable or is the cumbersome high expensive of preparation method, and industrialized production is difficult.
A kind of collaborative type flame-retardant sponge is mentioned in Chinese Patent Application No. 201711314789.8, by adjust formula and
Synergistic effect caused by the proportion of the different proportion of each based flame retardant, to improve the flame retardant property and reduction of sponge product
Influence of the fire retardant to the physical properties of sponge product.But this method is still addition fire retardant, and there are same drawbacks.
A kind of preparation method of phosphor-containing flame-proof polyether polyol is mentioned in Chinese Patent Application No. 201711015817.6, it should
Method uses traditional KOH alkali metal Catalytic processes, and this method complex steps, reaction time is long, and industrialized production is difficult,
And a kind of ignition-proof element is contained only, flame retardant effect is limited.
Summary of the invention
The object of the present invention is to provide a kind of flame retardant type sponge polyether polyol, and raw material is simple and easy to get, at low cost, knot
Structure is stablized, and anti-flammability is good；Invention also provides scientific and reasonable, simple and easy preparation methods.
Flame retardant type sponge polyether polyol of the present invention is with polyester 1000 and trihydroxy methyl phosphorous oxide (THPO)
For initiator, it is made fire-retardant with propylene oxide and epoxyethane ring-expansion polymerization using modified bimetallic cyanide complex catalyst
Type sponge polyether polyol.
The polyester 1000 is using melamine, formaldehyde, urea as the nitrogenous polyol of Material synthesis, function
Degree is 3.2, molecular weight 1000, is commercial product.
The trihydroxy methyl phosphorous oxide molecular weight is 124, is commercial product.
The molar ratio of the polyester 1000 and trihydroxy methyl phosphorous oxide is 1:3~3:1.
The ethylene oxide dosage is polyester 1000, trihydroxy methyl phosphorous oxide, propylene oxide, ethylene oxide quality sum
5-10%.
The modified bimetallic cyanide complex catalyst is commercial product, and dosage is polyester 1000, trihydroxy methyl oxygen
Change phosphorus, propylene oxide, ethylene oxide quality sum 0.002~0.01%.
The mass ratio of the propylene oxide and initiator is 2.5:1~7.5:1.
The hydroxyl value of the flame retardant type sponge polyether polyol is 54.5~57.5mgKOH/g.
The reaction temperature when polymerization is 130-145 DEG C.
The preparation method of the flame retardant type sponge polyether polyol, comprising the following steps:
Polyester 1000, trihydroxy methyl phosphorous oxide, modified bimetallic catalysts are added in autoclave, are warming up to
110~130 DEG C, vacuum degree -0.093MPa is kept, 0.5~2h of dehydration is vacuumized；Polyester 1000 and trihydroxy methyl phosphorous oxide is added
The propylene oxide of quality sum 5%~15% carries out induced activation reaction, and inducing temperature is 130 ± 2 DEG C, and induced pressure≤
0.2MPa；When reacting kettle inner pressure continues to decline and be down to negative pressure, temperature starts to continue to rise, show that polymerization reaction starts,
It is continuously added to propylene oxide and ethylene oxide is polymerize, 130-145 DEG C of reaction temperature；Continue aging reaction after charging
0.5~1h, then vacuumizes 1~2h of demonomerization, and cooling discharge obtains the flame retardant type sponge polyether polyol.
The invention has the following advantages:
(1) present invention selects suitable initiator, and nitrogen and phosphorus are introduced into molecular structure, made by cooperative flame retardant effect
Polyether polyol has anti-flammability, and compared with traditional additive flame retardant ingredient, the present invention is reaction-type flame-retarding ingredient, and structure is steady
Fixed, nitrogen and phosphorus cooperative flame retardant effect are good, are halogen-free, low-smoke low-toxicity when burning；
(2) polyether polyol equivalent provided by the present invention is consistent with traditional sponge polyether polyol, therefore is being formulated
When middle introducing polyether polyol of the present invention, it can replace with conventional polyether polyols equivalent and become without influencing formula index
Change, without calculating the dosage that adjustment B material is isocyanates, polyether polyol of the present invention is determined according to flame retardant property demand
With the ratio of conventional polyether polyols, formula adjustment is flexibly and easily；
(3) preparation method is simple described in, does not generate the three wastes, and production cost is low.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but it is not intended to limit implementation of the invention.
All raw materials used in embodiment are commercially available unless otherwise specified.
Embodiment 1
250g polyester 1000,93g trihydroxy methyl phosphorous oxide, 0.06g modified bimetallic are added in reaction kettle at room temperature to urge
Agent, the vacuum dehydration 2h at -0.093MPa, 110 DEG C；52g propylene oxide is added and carries out induced activation reaction, works as reaction unit
Internal pressure is insisted on to continue to be shown to have begun polymerization reaction, continuous feed propylene oxide 2432g when dropping to negative pressure, constant temperature rising
With ethylene oxide 149g, 140 DEG C of reaction temperature；Continue aging reaction 1h after charging, then vacuum is de- at -0.093MPa
Gas 1h discharges after being cooled to 80 DEG C, obtains target polyether polyol A.Specific test data is shown in Table 1.
Embodiment 2
750g polyester 1000,31g trihydroxy methyl phosphorous oxide, 0.32g modified bimetallic are added in reaction kettle at room temperature to urge
Agent, the vacuum dehydration 1h at -0.093MPa, 110 DEG C；39g propylene oxide is added and carries out induced activation reaction, works as reaction unit
Internal pressure is insisted on to continue to be shown to have begun polymerization reaction, continuous feed propylene oxide 2098g when dropping to negative pressure, constant temperature rising
With ethylene oxide 324g, 130 DEG C of reaction temperature；Continue aging reaction 0.5h after charging, then the vacuum at -0.093MPa
Deaerate 2h, discharges after being cooled to 80 DEG C, obtains target polyether polyol B.Specific test data is shown in Table 1.
Embodiment 3
500g polyester 1000,62g trihydroxy methyl phosphorous oxide, 0.19g modified bimetallic are added in reaction kettle at room temperature to urge
Agent, the vacuum dehydration 1.5h at -0.093MPa, 110 DEG C；56g propylene oxide is added and carries out induced activation reaction, when reaction fills
It sets internal pressure and insists on to continue and show to have begun polymerization reaction, continuous feed propylene oxide when dropping to negative pressure, constant temperature rising
2255g and ethylene oxide 233g, 135 DEG C of reaction temperature；Continue aging reaction 1h after charging, then at -0.093MPa
Vacuum outgas 1.5h discharges after being cooled to 80 DEG C, obtains target polyether polyol C.Specific test data is shown in Table 1.
Index test is carried out with polyether polyol to flame retardant type sponge made from embodiment 1-3, test result is shown in Table 1.
1 test result of table
Flammability test:
Specific formula see the table below
Sponge foam sample is made using high-speed stirred mixed foaming by above-mentioned formula.
Sample 1 is made with polyether polyol 5631 (commercial product) using conventional sponges, oxygen index (OI) is 21.8% after tested,
Do not have flame retardant property.
Sample 2 is made using target polyether polyol, oxygen index (OI) 27.2%, reaches B2 grades of flame-retardancy requirements, have after tested
Excellent flame retardant property.
Claims (10)
1. a kind of flame retardant type sponge polyether polyol, it is characterised in that: with polyester 1000 and trihydroxy methyl phosphorous oxide be starting
Flame retardant type sponge is made with propylene oxide and epoxyethane ring-expansion polymerization using modified bimetallic cyanide complex catalyst in agent
Use polyether polyol.
2. flame retardant type sponge polyether polyol according to claim 1, it is characterised in that: polyester 1000 is with melamine
Amine, formaldehyde, the nitrogenous polyol that urea is Material synthesis, degree of functionality 3.2, molecular weight 1000.
3. flame retardant type sponge polyether polyol according to claim 1, it is characterised in that: trihydroxy methyl phosphorous oxide molecule
Amount is 124.
4. flame retardant type sponge polyether polyol according to claim 1, it is characterised in that: polyester 1000 and trihydroxy methyl
The molar ratio of phosphorous oxide is 1:3~3:1.
5. flame retardant type sponge polyether polyol according to claim 1, it is characterised in that: ethylene oxide dosage is polyester
1000, the 5-10% of trihydroxy methyl phosphorous oxide, propylene oxide, ethylene oxide quality sum.
6. flame retardant type sponge polyether polyol according to claim 1, it is characterised in that: modified bimetallic cyaniding complexing
Object catalyst amount be polyester 1000, trihydroxy methyl phosphorous oxide, propylene oxide, ethylene oxide quality sum 0.002~
0.01%.
7. flame retardant type sponge polyether polyol according to claim 1, it is characterised in that: propylene oxide and initiator
Mass ratio is 2.5:1~7.5:1.
8. flame retardant type sponge polyether polyol according to claim 1, it is characterised in that: flame retardant type sponge polyethers is more
The hydroxyl value of first alcohol is 54.5~57.5mgKOH/g.
9. flame retardant type sponge polyether polyol according to claim 1, it is characterised in that: reaction temperature when polymerization is
130-145℃。
10. a kind of preparation method of any flame retardant type sponge polyether polyol of claim 1-9, it is characterised in that packet
Include following steps:
Polyester 1000, trihydroxy methyl phosphorous oxide, modified bimetallic catalysts are added in autoclave, it is warming up to 110~
130 DEG C, vacuum degree -0.093MPa is kept, 0.5~2h of dehydration is vacuumized；Polyester 1000 and trihydroxy methyl phosphorous oxide quality is added
The sum of 5%~15% propylene oxide carry out induced activation reaction, inducing temperature be 130 ± 2 DEG C, induced pressure≤0.2MPa；
When reacting kettle inner pressure continues to decline and be down to negative pressure, temperature starts to continue to rise, shows that polymerization reaction starts, be continuously added to
Propylene oxide and ethylene oxide are polymerize, and 130-145 DEG C of reaction temperature；Continue 0.5~1h of aging reaction after charging, so
After vacuumize 1~2h of demonomerization, cooling discharge obtains the flame retardant type sponge polyether polyol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811148261.2A CN109400866A (en) | 2018-09-29 | 2018-09-29 | Flame retardant type sponge polyether polyol and preparation method thereof |
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| CN201811148261.2A CN109400866A (en) | 2018-09-29 | 2018-09-29 | Flame retardant type sponge polyether polyol and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041689A (en) * | 2019-04-19 | 2019-07-23 | 天津企辰聚氨酯有限公司 | A kind of polyisocyanurate foam and preparation method thereof |
| 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 |
| CN115232287A (en) * | 2022-08-08 | 2022-10-25 | 南京金栖化工集团有限公司 | Flame-retardant slow-rebound polyurethane sponge and preparation method thereof |
| CN115304762A (en) * | 2022-08-11 | 2022-11-08 | 山东一诺威新材料有限公司 | Preparation method and application of reactive halogen-free flame-retardant polyether polyol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193934A (en) * | 2014-06-10 | 2014-12-10 | 方大锦化化工科技股份有限公司 | Preparing method of polymer polyol used for environmental friendly polyurethane block flexible foam |
| 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 |
| CN107141467A (en) * | 2017-06-28 | 2017-09-08 | 山东诺威新材料有限公司 | The preparation method of phosphorus chlorine composite flame-proof polyethers |
| CN107880261A (en) * | 2017-11-27 | 2018-04-06 | 山东诺威新材料有限公司 | High Reactive Flame Retardant Polyether Polyol and preparation method thereof |
-
2018
- 2018-09-29 CN CN201811148261.2A patent/CN109400866A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193934A (en) * | 2014-06-10 | 2014-12-10 | 方大锦化化工科技股份有限公司 | Preparing method of polymer polyol used for environmental friendly polyurethane block flexible foam |
| 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 |
| CN107141467A (en) * | 2017-06-28 | 2017-09-08 | 山东诺威新材料有限公司 | The preparation method of phosphorus chlorine composite flame-proof polyethers |
| CN107880261A (en) * | 2017-11-27 | 2018-04-06 | 山东诺威新材料有限公司 | High Reactive Flame Retardant Polyether Polyol and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李俊贤编: "《塑料工业手册 聚氨酯》", 31 July 1999 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041689A (en) * | 2019-04-19 | 2019-07-23 | 天津企辰聚氨酯有限公司 | A kind of polyisocyanurate foam and preparation method thereof |
| CN110041689B (en) * | 2019-04-19 | 2021-02-05 | 天津企辰聚氨酯有限公司 | Polyisocyanurate foam and preparation method thereof |
| 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 |
| CN115232287A (en) * | 2022-08-08 | 2022-10-25 | 南京金栖化工集团有限公司 | Flame-retardant slow-rebound polyurethane sponge and preparation method thereof |
| CN115304762A (en) * | 2022-08-11 | 2022-11-08 | 山东一诺威新材料有限公司 | Preparation method and application of reactive halogen-free flame-retardant polyether polyol |
| CN115304762B (en) * | 2022-08-11 | 2023-12-29 | 山东一诺威新材料有限公司 | Preparation method and application of reactive halogen-free flame-retardant polyether polyol |
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