CN107880261B - High-activity flame-retardant polyether polyol and preparation method thereof - Google Patents
High-activity flame-retardant polyether polyol and preparation method thereof Download PDFInfo
- Publication number
- CN107880261B CN107880261B CN201711205093.1A CN201711205093A CN107880261B CN 107880261 B CN107880261 B CN 107880261B CN 201711205093 A CN201711205093 A CN 201711205093A CN 107880261 B CN107880261 B CN 107880261B
- Authority
- CN
- China
- Prior art keywords
- polyether polyol
- flame
- retardant polyether
- activity
- retardant
- 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
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
- C08G65/2618—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
- 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
- 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
- C08G65/2642—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 characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2675—Phosphorus or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of polymer synthesis, and particularly relates to high-activity flame-retardant polyether polyol and a preparation method thereof. The high-activity flame-retardant polyether polyol is prepared by ring-opening polymerization of propylene oxide and ethylene oxide with PNR1000 and THPO as initiators under the action of a phosphazene catalyst. According to the invention, a hydroxyl compound PNR1000 with high nitrogen content and THPO with phosphorus and stable chemical structure are used as an initiator, and P, N two flame retardant elements are organically combined, so that the prepared polyether polyol has good flame retardance; the phosphazene catalyst is selected, so that the catalytic reaction activity is high, the catalytic effect is good, the period is short, the efficiency is high, and the stability of the prepared product is good; the prepared high-activity flame-retardant polyether polyol is a high-molecular-weight light-yellow transparent liquid suitable for the field of soft foams, and a flame-retardant system does not contain halogen, so that the environment is protected; the preparation method has the advantages of short reaction time and high conversion efficiency.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to high-activity flame-retardant polyether polyol and a preparation method thereof.
Background
The polyurethane material has wide application range, but has the defects of poor flame retardant property and easy combustion. Polyether polyol is one of main raw materials for preparing polyurethane materials, and the performance of the polyether polyol determines the application range of the polyurethane materials. Currently, in the field of flame retardation, the emerging flame-retardant polymer polyol has a good flame-retardant effect, but the composition is complex, and the state is milky white, which greatly limits the application of the flame-retardant polymer polyol in polyurethane materials.
The flame retardance of the existing polyurethane products is divided into additive flame retardance and reactive flame retardance. The additive type flame retardant is added in a physical mode, flame retardant components do not participate in reaction, and a good flame retardant effect can be obtained, but the mechanical property and the processing technology property of the base material are greatly damaged in the formula, and the flame retardant can migrate along with the prolonging of time and is separated out from the polyurethane material, so that the flame retardance of the polyurethane material is gradually reduced, and even the flame retardant effect is lost. The reactive flame retardance is connected into a molecular chain of a polyurethane material in a chemical reaction mode, the mode has little damage to the performance of a base material, and the flame retardance is durable, so that the reactive flame retardance is the mainstream trend of the current flame retardance field. However, the preparation of the current high molecular weight flame-retardant polyether has a series of problems of high technical barrier, high synthesis difficulty, poor flame-retardant effect or halogen contained in a flame-retardant system and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the high-activity flame-retardant polyether polyol which has the characteristics of excellent flame-retardant property and no halogen in a flame-retardant system; the preparation method provided by the invention is green and environment-friendly, and has short reaction time and high conversion efficiency.
The high-activity flame-retardant polyether polyol is prepared by ring-opening polymerization of propylene oxide and ethylene oxide by taking PNR1000 and THPO as initiators under the action of a phosphazene catalyst.
Wherein:
the hydroxyl value of the high-activity flame-retardant polyether polyol is 88.0-92.0 mgKOH/g.
The PNR1000 is a nitrogen-containing polyhydroxy compound synthesized by taking melamine, formaldehyde and urea as raw materials, has the functionality of 3.2 and the molecular weight of 1000, and is a product sold in China general chemical engineering (Kunshan) Co.
The mol ratio of PNR1000 to THPO is 2: 3-3: 1.
the mass ratio of the propylene oxide to the ethylene oxide is 50: 40-50: 10.
the phosphazene catalyst is a product sold by Shanghai petrochemical engineering research institute of China petrochemical company Limited.
The usage amount of the phosphazene catalyst is 0.1-0.3% of the total mass of the initiator, the propylene oxide and the ethylene oxide.
The preparation method of the high-activity flame-retardant polyether polyol comprises the following steps:
(1) adding an initiator and a phosphazene catalyst into a high-pressure reaction kettle, replacing nitrogen until the oxygen content is less than or equal to 50ppm, heating to 90-110 ℃, and keeping the vacuum degree at-0.095 MPa for vacuum pumping and dehydrating for 0.5-2 h;
(2) controlling the temperature to be 88-92 ℃, adding part of propylene oxide for reaction, controlling the temperature to be 90-110 ℃ after the addition, continuously adding the rest propylene oxide for polymerization reaction, and continuing the aging reaction after the addition;
(3) controlling the temperature to be 105-115 ℃, continuously adding ethylene oxide for polymerization reaction, continuing aging reaction after adding the ethylene oxide, vacuumizing to remove monomers, cooling and discharging to obtain the product.
Wherein:
in the step (2), the temperature is controlled to be 88-92 ℃, and an initiator, a catalyst, propylene oxide and propylene oxide accounting for 5-15% of the total mass of ethylene oxide are added for reaction.
And (3) the continuous aging reaction time in the step (2) is 2-4 h.
And (4) continuously aging for 1-2 h, and vacuumizing for 1-2 h to remove the monomer.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, a hydroxyl compound PNR1000 with high nitrogen content and THPO with phosphorus and stable chemical structure are used as an initiator, and P, N two flame retardant elements are organically combined, so that the prepared polyether polyol has good flame retardance.
2. The high-activity flame-retardant polyether polyol is prepared by using the phosphazene catalyst, so that the catalytic reaction activity is high, the catalytic effect is good, the period is short, the efficiency is high, and the stability of the prepared product is good.
3. The high-activity flame-retardant polyether polyol prepared by the invention is a high-molecular-weight light-yellow transparent liquid suitable for the field of soft foams, and a flame-retardant system does not contain halogen, so that the high-activity flame-retardant polyether polyol is green and environment-friendly.
4. The preparation method disclosed by the invention is environment-friendly, short in reaction time and high in conversion efficiency.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
1) Adding weighed initiator PNR 1000500 kg, THPO 62kg and phosphazene catalyst 2.2kg into a high-pressure reaction kettle, replacing with nitrogen until the oxygen content is less than or equal to 50ppm, heating to 90 ℃, keeping the vacuum degree at-0.095 MPa, and vacuumizing and dehydrating for 0.5 h;
2) controlling the temperature to 88 ℃, adding 110kg of Propylene Oxide (PO) for reaction; after the feeding is finished, heating to 95 ℃, continuously adding 800kg of PO for polymerization, and after the feeding is finished, continuing the aging reaction for 2 hours;
3) and (3) heating to 105 ℃, continuously adding 728kg of Ethylene Oxide (EO) for polymerization, continuing the aging reaction for 1h after the feeding is finished, vacuumizing to remove the monomer for 2h, and cooling and discharging.
Example 2
(1) Adding weighed initiator PNR 1000750 kg and THPO 31kg and phosphazene catalyst 6.6kg into a high-pressure reaction kettle, replacing with nitrogen until the oxygen content is less than or equal to 50ppm, heating to 100 ℃, and keeping the vacuum degree of-0.095 MPa for vacuum pumping and dehydration for 1 h;
2) controlling the temperature to be 90 ℃, adding 330kg of Propylene Oxide (PO) for reaction; after the feeding is finished, heating to 100 ℃, continuously adding PO 852.5kg for polymerization, and after the feeding is finished, continuing the aging reaction for 3 hours;
3) heating to 115 ℃, continuously adding 236.5kg of Ethylene Oxide (EO) for polymerization, continuing the aging reaction for 2h after the feeding is finished, vacuumizing to remove the monomer for 1h, cooling and discharging.
Example 3
1) Putting weighed initiator PNR 1000400 kg and THPO 74.4kg and phosphazene catalyst 4.4kg into a high-pressure reaction kettle, replacing with nitrogen until the oxygen content is less than or equal to 50ppm, heating to 110 ℃, and keeping the vacuum degree at-0.095 MPa for vacuum pumping and dehydration for 2 h;
2) controlling the temperature to be 92 ℃, adding 220kg of Propylene Oxide (PO) for reaction; after the feeding is finished, heating to 108 ℃, continuously adding 1012kg of PO for polymerization, and after the feeding is finished, continuing the aging reaction for 4 hours;
3) heating to 105 deg.C, continuously adding 493kg of Ethylene Oxide (EO) for polymerization, continuing aging reaction for 2h after the addition is completed, vacuumizing to remove monomer for 1.5h, cooling and discharging.
The high activity flame retardant polyether polyols obtained in examples 1-3 were subjected to performance tests, and the test results are shown in Table 1.
TABLE 1 test results
And (3) testing the flame retardant property:
taking polyether polyol INOVOL-F56390 parts, silicone oil 2 parts, calcium carbonate 20 parts, A10.2 parts, A330.4 parts, water 3 parts and isocyanate 82 parts, stirring at a high speed, mixing and foaming to prepare a polyurethane foam product, and performing flame retardant property test by taking the polyurethane foam product as a blank control group, wherein the oxygen index is 22%.
The high activity flame retardant polyether polyol prepared in example 1 was used in place of 20 parts of polyether polyol INOVOL-F5631. Taking polyether polyol INOVOL-F5630 parts, high-activity flame-retardant polyether polyol 20 parts, silicone oil 2 parts, calcium carbonate 20 parts, A10.2 parts, A330.4 parts, water 3 parts and isocyanate 85 parts, stirring at a high speed, mixing and foaming to prepare a polyurethane foam product, taking the polyurethane foam product as an experimental group, and carrying out flame retardant property test, wherein the oxygen index is 28.5%.
In conclusion, the high-activity flame-retardant polyether polyol prepared by the method has excellent flame-retardant performance.
Claims (8)
1. A high-activity flame-retardant polyether polyol is characterized in that: under the action of a phosphazene catalyst, PNR1000 and THPO are used as initiators and are subjected to ring-opening polymerization with epoxypropane and epoxyethane to prepare high-activity flame-retardant polyether polyol;
the mol ratio of PNR1000 to THPO is 2: 3-3: 1;
the mass ratio of the propylene oxide to the ethylene oxide is 50: 40-50: 10.
2. the highly reactive flame retardant polyether polyol according to claim 1, characterized in that: the hydroxyl value of the high-activity flame-retardant polyether polyol is 88.0-92.0 mgKOH/g.
3. The highly reactive flame retardant polyether polyol according to claim 1, characterized in that: the PNR1000 is a nitrogen-containing polyhydroxy compound synthesized by taking melamine, formaldehyde and urea as raw materials, the functionality of the nitrogen-containing polyhydroxy compound is 3.2, and the molecular weight of the nitrogen-containing polyhydroxy compound is 1000.
4. The highly reactive flame retardant polyether polyol according to claim 1, characterized in that: the usage amount of the phosphazene catalyst is 0.1-0.3% of the total mass of the initiator, the propylene oxide and the ethylene oxide.
5. A process for preparing a highly reactive flame retardant polyether polyol as claimed in any one of claims 1 to 4, wherein: the method comprises the following steps:
(1) adding an initiator and a phosphazene catalyst into a high-pressure reaction kettle, replacing nitrogen until the oxygen content is less than or equal to 50ppm, heating to 90-110 ℃, and keeping the vacuum degree at-0.095 MPa for vacuum pumping and dehydrating for 0.5-2 h;
(2) controlling the temperature to be 88-92 ℃, adding part of propylene oxide for reaction, controlling the temperature to be 90-110 ℃ after the addition, continuously adding the rest propylene oxide for polymerization reaction, and continuing the aging reaction after the addition;
(3) controlling the temperature to be 105-115 ℃, continuously adding ethylene oxide for polymerization reaction, continuing aging reaction after adding the ethylene oxide, vacuumizing to remove monomers, cooling and discharging to obtain the product.
6. The method for preparing the high-activity flame-retardant polyether polyol according to claim 5, wherein the method comprises the following steps: in the step (2), the temperature is controlled to be 88-92 ℃, and an initiator, a catalyst, propylene oxide and propylene oxide accounting for 5-15% of the total mass of ethylene oxide are added for reaction.
7. The method for preparing the high-activity flame-retardant polyether polyol according to claim 5, wherein the method comprises the following steps: and (3) the continuous aging reaction time in the step (2) is 2-4 h.
8. The method for preparing the high-activity flame-retardant polyether polyol according to claim 5, wherein the method comprises the following steps: and (4) continuously aging for 1-2 h, and vacuumizing for 1-2 h to remove the monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711205093.1A CN107880261B (en) | 2017-11-27 | 2017-11-27 | High-activity flame-retardant polyether polyol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711205093.1A CN107880261B (en) | 2017-11-27 | 2017-11-27 | High-activity flame-retardant polyether polyol and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107880261A CN107880261A (en) | 2018-04-06 |
| CN107880261B true CN107880261B (en) | 2020-05-22 |
Family
ID=61775311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711205093.1A Active CN107880261B (en) | 2017-11-27 | 2017-11-27 | High-activity flame-retardant polyether polyol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107880261B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110862526B (en) * | 2019-11-01 | 2022-12-06 | 上海应用技术大学 | Preparation method of high-activity flame-retardant polyether polyol |
| CN111004379B (en) * | 2019-12-02 | 2022-03-15 | 浙江理工大学桐乡研究院有限公司 | Preparation method of flame-retardant polyol with high phosphorus content and multiple functionality degrees |
| 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 |
| CN112646161B (en) * | 2020-12-14 | 2022-11-29 | 山东一诺威新材料有限公司 | Full sucrose type flame-retardant polyether polyol 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 |
| CN115232287B (en) * | 2022-08-08 | 2023-07-14 | 南京金栖化工集团有限公司 | Flame-retardant slow-rebound polyurethane sponge and preparation method thereof |
-
2017
- 2017-11-27 CN CN201711205093.1A patent/CN107880261B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107880261A (en) | 2018-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107880261B (en) | High-activity flame-retardant polyether polyol and preparation method thereof | |
| CN104974326B (en) | A kind of composition for preparing non yellowing flexible polyurethane foams, non yellowing flexible polyurethane foams and preparation method thereof | |
| CN1235942C (en) | Process for production of polyol blends | |
| CN102875791B (en) | Flame retardant soft foam polyether polyol and synthesis method thereof | |
| CN110885435A (en) | Process for preparing high functionality polyether polyols | |
| CN105330830B (en) | A kind of end alkenyl unsaturated polyether and application thereof | |
| CN109651609B (en) | Preparation method of polyether polyol with high EO content | |
| CN102731768A (en) | Method for preparing polyether glycol by using melamine as initiator | |
| CN105585707A (en) | Synthetic method of flame-retardation hard foam polyether polyol | |
| ES2388990T3 (en) | Procedure for the production of polyols | |
| CN109467690A (en) | A kind of flame-retardant polyether glycol and its preparation method and application | |
| CN107513157A (en) | Amido PPG and its preparation method and application | |
| CN111019113A (en) | Aminopolyether polyol for pure LBA system, preparation method thereof and polyurethane rigid foam prepared by using aminopolyether polyol | |
| CN114230782A (en) | Preparation method of bio-based polyether polyol | |
| CN113980264B (en) | Preparation method and application of flame-retardant polyether polyol | |
| CN102617848A (en) | Method for preparing sorbitol polyether polyol | |
| CN104311790A (en) | Formula used for synthesizing NDI-based polyurethane microcellular elastomer | |
| CN109306056B (en) | Reactive flame-retardant polyether polyol for OCF joint sealing adhesive and preparation method thereof | |
| CN112759752B (en) | Polyether polyol for synergistic flame-retardant sponge and preparation method thereof | |
| CN112646165B (en) | Preparation method and application of halogen-free flame-retardant polyether polyol | |
| CN104497298B (en) | Method for preparing polyether polyol with low degree of unsaturation, high molecular weight and high activity | |
| CN103951798A (en) | Polycarboxylate dispersant and its preparation method | |
| CN112661932A (en) | Spraying type environment-friendly rigid polyurethane foam raw material composition for pipeline | |
| CN111004363A (en) | Preparation method of toluene diisocyanate and hexamethylene diisocyanate mixed trimer curing agent | |
| CN104497046B (en) | Organic alkoxide and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |