CN114539188A - Preparation method and application of polyurethane foam anti-aging agent - Google Patents
Preparation method and application of polyurethane foam anti-aging agent Download PDFInfo
- Publication number
- CN114539188A CN114539188A CN202210075065.7A CN202210075065A CN114539188A CN 114539188 A CN114539188 A CN 114539188A CN 202210075065 A CN202210075065 A CN 202210075065A CN 114539188 A CN114539188 A CN 114539188A
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- Prior art keywords
- polyurethane foam
- aging agent
- polyisocyanate
- catalyst
- aging
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/205—Compounds containing groups, e.g. carbamates
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method and application of an anti-aging agent for polyurethane foam. Then, polyether, a foam stabilizer, a catalyst, a foaming agent and the anti-aging agent are mixed according to the mass ratio of 100: 4: 0.02: 0.2: 1, uniformly mixing to prepare a component A, and then mixing the component A and an isocyanate group-containing substance according to a mass ratio of 1: 1, stirring for 30-40 seconds under the conditions of normal temperature and normal pressure, and pouring into a mould after stirring to prepare the polyurethane foam. According to the invention, by preparing the micromolecules containing a large number of rigid structures and epoxy groups and adding the micromolecules into the polyurethane foam, epoxy functional groups can react with the polyurethane foam along with the time when the polyurethane foam is degraded, so that the crosslinking degree is increased, and the performance attenuation of the polyurethane foam is relieved.
Description
Technical Field
The invention belongs to the technical field of polyurethane foam, and particularly relates to a preparation method and application of an anti-aging agent for polyurethane foam.
Background
The foam is one of the main varieties of polyurethane synthetic materials, and is mainly characterized by porosity, so that the relative density is small and the specific strength is high. The polyurethane foam plastic has wide application range, almost permeates all departments of national economy, is very common in furniture, bedding, transportation, refrigeration, building, heat insulation and other departments, and becomes one of indispensable materials.
The common polyurethane foam is prepared by the reaction of polyether polyol and MDI, some foaming agents are compounded, the skeleton of the polyurethane foam is formed by the reaction and crosslinking of isocyanate groups and active hydrogen, however, the skeleton of the polyurethane foam is degraded along with the lapse of time in the use process, the crosslinking degree of the polyurethane foam is reduced, and the performance is also reduced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method and application of a polyurethane foam anti-aging agent.
The technical scheme adopted by the invention is as follows: a preparation method of an anti-aging agent for polyurethane foam comprises the following specific steps: adding a catalyst into polyisocyanate, S-glycidol and an organic solvent under the protection of inert gas, stirring for reaction, and vacuumizing at the reaction temperature to remove the organic solvent after the reaction is finished.
Preferably, the reaction temperature is (55-65) DEG C, and the reaction time is (8-9) h.
Preferably, the molar ratio of the polyisocyanate to the S-glycidol is 1 (2.9-3.1).
Preferably, the organic solvent is one of ethyl acetate, toluene and xylene, and the weight of the organic solvent is 50-100% of the total weight of the polyisocyanate and the S-glycidol.
Preferably, the polyisocyanate is one of HDI biuret, HDI trimer, TDI trimer and IPDI trimer.
Preferably, the catalyst is one of dibutyltin dilaurate or dibutyltin dichloride.
Preferably, the catalyst is used in an amount of one ten thousandth to five ten thousandth of the sum of the weight of the polyisocyanate and the S-glycidol.
The application of the polyurethane foam anti-aging agent comprises the following specific steps: polyether, a foam stabilizer, a catalyst, a foaming agent and the anti-aging agent are mixed according to the mass ratio of 100: (1-4): (0.02-0.1): (0.2-0.4): (1-4) uniformly mixing to prepare a component A, and then mixing the component A with the substance containing isocyanate groups according to the mass ratio of 1: 1, stirring for 30-40 seconds under the conditions of normal temperature and normal pressure, and pouring into a mould after stirring to prepare the polyurethane foam.
Preferably, the polyether is polyether triol, and can be polyether triol with molecular weight of 400; the catalyst is dibutyltin dilaurate, the foaming agent is water, the foam stabilizer is silicone oil, and the substance containing isocyanate groups is polymethylene polyphenyl polyisocyanate.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, by preparing the micromolecules containing a large number of rigid structures and epoxy groups and adding the micromolecules into the polyurethane foam, epoxy functional groups can react with the polyurethane foam along with the time when the polyurethane foam is degraded, so that the crosslinking degree is increased, and the performance attenuation of the polyurethane foam is relieved.
2. According to the invention, hydroxyl on S-glycidol is used for blocking trifunctional isocyanate to prepare micromolecule containing about three epoxy functional groups, and the micromolecule can slowly react with carbamate in the later stage to relieve the performance attenuation of polyurethane foam.
3. The invention adopts a vacuum pumping mode to remove the solvent, prevents heat release in the polyurethane foam forming process, enables the solvent to volatilize to form gas, and causes the foam density to be out of control.
4. The reaction temperature of the invention is (55-65) DEG C, which is selected because the solvent and the S-glycidol are easy to volatilize when the temperature is too high, and the reaction time is too long when the temperature is too low. The reaction time of the invention is (8-9) h, if the reaction time is too short, the reaction is incomplete, S-glycidol is lost during vacuumizing, and the strength of polyurethane foam is adversely affected.
Detailed Description
In order that those skilled in the art will be able to better understand the technical solutions provided by the present invention, the following description is provided in connection with specific embodiments.
Example 1
Adding 478g of Hexamethylene Diisocyanate (HDI) biuret, 222g of S-glycidol and 700g of ethyl acetate into 0.07g of dibutyltin dilaurate as a catalyst under the protection of nitrogen at 60 ℃, stirring for reacting for 8 hours, continuously vacuumizing to remove the solvent, pouring into a glass bottle, and hermetically storing to prepare the anti-aging agent; uniformly mixing 1g of the anti-aging agent, 100g of 400-molecular-weight polyether triol (YD 304), 0.2g of water, a foam stabilizer and a catalyst to prepare a component A, and then mixing the component A with a substance containing an isocyanate group, such as polymethylene polyphenyl polyisocyanate, according to a mass ratio of 1: 1, stirring for 30 seconds at normal temperature and normal pressure at the rotating speed of 200r/min, and pouring into a mold after stirring to prepare the polyurethane foam.
Example 2
Adding 504g of HDI tripolymer, 222g of S-glycidol and 726g of ethyl acetate into 0.09g of dibutyltin dilaurate serving as a catalyst under the protection of nitrogen at 60 ℃, stirring for reacting for 8 hours, continuously vacuumizing to remove the solvent, pouring into a glass bottle, and sealing for storage to prepare the anti-aging agent; uniformly mixing 2g of the anti-aging agent, 100g of YD304, 0.2g of water, a foam stabilizer and a catalyst to prepare a component A, and then mixing the component A with polymethylene polyphenyl polyisocyanate according to a mass ratio of 1: 1, stirring for 30 seconds at normal temperature and normal pressure at the rotating speed of 200r/min, and pouring into a mold after stirring to prepare the polyurethane foam.
Comparative example 1
Uniformly mixing 100g of YD304, 0.2g of water, a foam stabilizer and a catalyst to prepare a component A, and then mixing the component A with polymethylene polyphenyl polyisocyanate according to a mass ratio of 1: 1, stirring for 30 seconds at normal temperature and normal pressure at the rotating speed of 200r/min, and pouring into a mold after stirring to prepare the polyurethane foam.
TABLE 1 compressive Strength of polyurethane foams
| Test specimen | Standard condition 7 days strength (MPa) | Standard condition of 7 days plus high temperature and high humidity 7 days strength (MPa) |
| Comparative example 1 | 7.1 | 6.2 |
| Example 1 | 7.0 | 7.4 |
| Example 2 | 7.1 | 7.6 |
As can be seen from Table 1, after the anti-aging agent is added, the foam performance has obvious advantages compared with the common foam performance after the treatment under the high-temperature and high-humidity conditions, which shows that the anti-aging agent can play a role in resisting the decay of the polyurethane foam performance with time. After the anti-aging agent is added, under the condition of high temperature and high humidity, the epoxy group and the polyurethane foam slowly react, the crosslinking degree is improved, and the strength is improved.
Claims (10)
1. The preparation method of the polyurethane foam anti-aging agent is characterized by comprising the following specific steps: adding a catalyst into polyisocyanate, S-glycidol and an organic solvent under the protection of inert gas, stirring for reaction, and vacuumizing at the reaction temperature to remove the organic solvent after the reaction is finished.
2. The method for preparing the polyurethane foam anti-aging agent according to claim 1, wherein the reaction temperature is 55-65 ℃ and the reaction time is 8-9 hours.
3. The method of preparing the polyurethane foam aging inhibitor according to claim 1, wherein the molar ratio of the polyisocyanate to the S-glycidol is 1:2.9 to 3.1.
4. The method of claim 1, wherein the organic solvent is one of ethyl acetate, toluene and xylene, and the weight of the organic solvent is 50% to 100% of the total weight of the polyisocyanate and the S-glycidol.
5. The method of preparing the polyurethane foam anti-aging agent according to claim 1, wherein the polyisocyanate is one of HDI biuret, HDI trimer, TDI trimer, IPDI trimer.
6. The method of claim 1, wherein the catalyst is dibutyltin dilaurate or dibutyltin dichloride.
7. The method of preparing the polyurethane foam aging resistor as claimed in claim 1, wherein the catalyst is used in an amount of one ten thousandth to five ten thousandth of the sum of the weight of the polyisocyanate and the weight of the S-glycidol.
8. An anti-aging agent for polyurethane foam, which is obtained by the method of any one of claims 1 to 7.
9. The use of the polyurethane foam aging inhibitor according to claim 8, characterized by comprising the following steps: polyether, a foam stabilizer, a catalyst, a foaming agent and the anti-aging agent are mixed according to the mass ratio of 100: (1-4): (0.02-0.1): (0.2-0.4): (1-4) uniformly mixing to prepare a component A, and then mixing the component A with the substance containing isocyanate groups according to the mass ratio of 1: 1, stirring for 30-40 seconds under the conditions of normal temperature and normal pressure, and pouring into a mould after stirring to prepare the polyurethane foam.
10. The use of the polyurethane foam aging resistor as claimed in claim 9, wherein the polyether is polyether triol, the catalyst is dibutyltin dilaurate, the foaming agent is water, the foam stabilizer is silicone oil, and the isocyanate group-containing substance is polymethylene polyphenyl polyisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210075065.7A CN114539188A (en) | 2022-01-22 | 2022-01-22 | Preparation method and application of polyurethane foam anti-aging agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210075065.7A CN114539188A (en) | 2022-01-22 | 2022-01-22 | Preparation method and application of polyurethane foam anti-aging agent |
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| Publication Number | Publication Date |
|---|---|
| CN114539188A true CN114539188A (en) | 2022-05-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210075065.7A Pending CN114539188A (en) | 2022-01-22 | 2022-01-22 | Preparation method and application of polyurethane foam anti-aging agent |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040068022A1 (en) * | 2000-03-17 | 2004-04-08 | Yoshihiro Katsumata | Flexible polyurethane foam |
| CN103923322A (en) * | 2014-02-20 | 2014-07-16 | 上海大学 | Epoxy/polyurethane/organosilicon HB-LED packaging material preparation method |
| CN111635499A (en) * | 2020-06-05 | 2020-09-08 | 西安增材制造国家研究院有限公司 | Epoxy modified polyurethane resin, system, preparation method and application thereof |
-
2022
- 2022-01-22 CN CN202210075065.7A patent/CN114539188A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040068022A1 (en) * | 2000-03-17 | 2004-04-08 | Yoshihiro Katsumata | Flexible polyurethane foam |
| CN103923322A (en) * | 2014-02-20 | 2014-07-16 | 上海大学 | Epoxy/polyurethane/organosilicon HB-LED packaging material preparation method |
| CN111635499A (en) * | 2020-06-05 | 2020-09-08 | 西安增材制造国家研究院有限公司 | Epoxy modified polyurethane resin, system, preparation method and application thereof |
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