Non-polyurethane foam material and preparation method thereof
Non-polyurethane foam materials were prepared by polymerizing and foaming dimercaptothiadiazole materials with phenylenediene, which solved the shortcomings of existing materials in terms of foaming rate and cost, and achieved high foaming rate and strong pressure resistance.
Patent Information
- Application Number
- CN202610044820.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-14
- Publication Date
- 2026-03-17
AI Technical Summary
Existing foaming materials cannot simultaneously meet the requirements of high foaming rate, strong pressure resistance and low cost, especially chemically foamed polystyrene, which has the problems of low foaming rate and high price.
A non-polyurethane foam material was prepared by polymerizing and foaming dimercaptothiadiazole materials with styrene under nitrogen atmosphere and using 2,3-dithio(2-mercapto)-1-propanethiol and 2,2'-azobisisobutyronitrile as crosslinking agents.
It achieves high foaming rate and good compression resistance, while reducing material density and cost. The material exhibits excellent strain performance under pressure.
Smart Images
Figure CN121673567A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of foamed materials, and relates to a non-polyurethane foamed material, and also relates to a preparation method of the non-polyurethane foamed material. BACKGROUND
[0002] Foamed materials are a kind of materials that realize lightness, buffering, heat insulation and other functions through a porous structure, and have been widely used in packaging protection, building insulation, traffic sound insulation and other fields. Currently, the most common foamed materials on the market are polyurethane (PU), polystyrene (EPS / XPS), polyethylene (PE) and phenolic (PF), and the core technical indicators mainly include density (generally 10-100 kg / m3), closed cell rate (high-quality products can reach more than 90%, directly affecting the heat insulation and waterproof effect), compressive strength (0.1-2.0 MPa), thermal conductivity (0.020-0.045 W / (m K) and temperature resistance range (different materials have large differences, and the temperature resistance range is about -50℃ to 150℃). They have their own advantages and disadvantages: PU foamed material has good flexibility and strong bonding force, but poor high-temperature resistance; EPS / XPS has low cost and good heat insulation effect, but is brittle and easy to age; PE foamed material is environmentally friendly and non-toxic, and has good chemical corrosion resistance, but has insufficient mechanical strength; phenolic foamed material has excellent flame retardance and high-temperature resistance, but has high brittleness and complex forming process.
[0003] Chemical foaming polystyrene is a foamed material formed by the decomposition of a chemical foaming agent to produce gas, so that the polystyrene (PS) matrix forms a porous structure, and the foaming rate is usually 1.2-2.8 times. The core is used for injection / molding of structural parts. However, the chemical foaming polystyrene has low foaming rate and high cost compared with physical foaming. How to solve the problems of low foaming rate (1.2-2.8) and high price of chemical foaming polystyrene has become an obstacle to its development. SUMMARY
[0004] The purpose of the present application is to provide a preparation method of a non-polyurethane foamed material, which solves the problem that the existing foamed material is difficult to simultaneously meet the requirements of high foaming rate, strong pressure-bearing capacity and low cost.
[0005] Another purpose of the present application is to provide a non-polyurethane foamed material.
[0006] The first technical solution adopted by the present application is a preparation method of a non-polyurethane foamed material, which specifically includes the following steps: Step 1: reacting and dissolving a dimercaptothiadiazole material; Step 2: adding the mixture treated in step 1 to divinylbenzene for polymerization and foaming.
[0007] The first technical solution of the present application is also characterized in that: The specific process of step 1 is: under the nitrogen environment, the dimercaptothiadiazole material, the divinylbenzene, 2,3-dithio(2-mercapto)-1-propane thiol and 2,2'-azobis isobutyronitrile are poured into a flask and stirred.
[0008] In step 1, the dimercaptothiadiazole material is one of dimercaptothiadiazole or dimercaptothiadiazole dimer.
[0009] In step 1, the divinylbenzene is one of 1,3-diisopropenylbenzene or 1,3-divinylbenzene.
[0010] In step 1, the mass ratio of the dimercaptothiadiazole material, the divinylbenzene and 2,3-dithio(2-mercapto)-1-propane thiol is 0.8-1.2:1:1.8-2.2.
[0011] In step 1, the stirring temperature is 50-80℃, and the stirring time is 30-90min.
[0012] The specific process of step 2 is: the mixture after the reaction of step 1 is added with divinylbenzene again under the nitrogen atmosphere, and the stirring is continued.
[0013] In step 2, the mass ratio of the product of step 1 and the divinylbenzene is 1:0.4-0.6.
[0014] In step 2, the stirring temperature is 50-80℃, and the stirring time is 6-14h.
[0015] The second technical solution adopted by the present application is the non-polyurethane foaming material prepared by the above preparation method of the non-polyurethane foaming material.
[0016] The beneficial effects of the present application are that the dimercaptothiadiazole or dimercaptothiadiazole dimer and 1,3-diisopropenylbenzene or 1,3-divinylbenzene are selected as the reaction main body, and 2,3-dithio(2-mercapto)-1-propane thiol is used as the crosslinking agent to realize the material foaming. The method is simple to operate, the equipment requirement is low, the obtained product has low density, high foaming rate, good compression resistance and low price. BRIEF DESCRIPTION OF DRAWINGS
[0017] Figure 1 is the compression resistance test process diagram of the foaming material prepared by the preparation method of the non-polyurethane foaming material of the present application, Figure 1 (a) is a top view of the foaming material, Figure 1 (b) is a side view of the foaming material, Figure 1 (c) is a side view of the foaming material after 200g pressure is applied. DETAILED DESCRIPTION
[0018] The specific embodiments will be described in detail below.
[0019] The preparation method of the non-polyurethane foaming material of the present application mainly comprises the reaction of dimercaptothiadiazole / dimercaptothiadiazole dimer and 1,3-diisopropenylbenzene / 1,3-divinylbenzene to prepare the foaming material, and the specific steps are as follows: Step 1, dissolving dimercaptothiadiazole materials; The specific process of step 1 is: under the nitrogen environment, the dimercaptothiadiazole materials, divinylbenzene, 2,3-dithio(2-mercapto)-1-propane thiol and 2,2'-azobis isobutyronitrile are poured into a flask and stirred.
[0020] In step 1, the dimercaptothiadiazole materials are dimercaptothiadiazole or dimercaptothiadiazole dimer, the divinylbenzene is 1,3-diisopropenylbenzene or 1,3-divinylbenzene, the mass ratio of dimercaptothiadiazole materials, 2,3-dithio(2-mercapto)-1-propane thiol and divinylbenzene is 0.8-1.2:1:0.8-1.2, the amount of 2,2'-azobis isobutyronitrile is 20-30 mg, the temperature is 50-80℃, and the time is 30-90 min.
[0021] Step 2, the mixture treated in step 1 is added to divinylbenzene for polymerization and foaming.
[0022] The specific process of step 2 is: the mixture after step 1 reaction is added with divinylbenzene again under the nitrogen atmosphere and continues to be stirred. The divinylbenzene is one of 1,3-diisopropenylbenzene or 1,3-divinylbenzene.
[0023] In step 2, the mass ratio of step 1 product and divinylbenzene is 1:0.4-0.6, the temperature is 50-80℃, and the time is 6-14 h.
[0024] Example 1 In a flask, 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithio(2-mercapto)-1-propane thiol, 0.25 g of 1,3-divinylbenzene and 20 mg of 2,2'-azobis isobutyronitrile are added, stirred at 65℃ under the nitrogen atmosphere for 0.5 h. After the mixture is clarified, 0.5 g of 1,3-divinylbenzene is added again and stirred at 65℃ for 8 h, and the foaming is completed.
[0025] Example 2 In a flask, 0.2 g of dimercaptothiadiazole, 0.5 g of 2,3-dithio(2-mercapto)-1-propane thiol, 0.4 g of 1,3-diisopropenylbenzene and 20 mg of 2,2'-azobis isobutyronitrile are added, stirred at 65℃ under the nitrogen atmosphere for 0.5 h. After the mixture is clarified, 0.4 g of 1,3-diisopropenylbenzene is added again and stirred at 65℃ for 8 h, and the foaming is completed.
[0026] Example 3 In a flask, 0.3 g of dimercaptothiadiazole, 0.5 g of 2,3-dithio(2-mercapto)-1- propane sulfide, 0.6 g of 1,3-diisopropenylbenzene and 20 mg of 2,2'-azobisisobutyronitrile were added, and stirred at 65°C for 0.5 h under nitrogen atmosphere. After the mixture was clarified, 0.6 g of 1,3-diisopropenylbenzene was added again, and stirred at 65°C for 8 h again, and the foaming was completed.
[0027] Example 4 In a flask, 0.5 g of dimercaptothiadiazole dimer, 1 g of 2,3-dithio(2-mercapto)-1- propane sulfide, 0.5 g of 1,3-diisopropenylbenzene and 30 mg of 2,2'-azobisisobutyronitrile were added, and stirred at 65°C for 1 h under nitrogen atmosphere. After the mixture was clarified, 1 g of 1,3-diisopropenylbenzene was added again, and stirred at 65°C for 12 h again, and the foaming was completed.
[0028] Example 5 In a flask, 0.4 g of dimercaptothiadiazole dimer, 1 g of 2,3-dithio(2-mercapto)-1- propane sulfide, 0.4 g of 1,3-divinylbenzene and 30 mg of 2,2'-azobisisobutyronitrile were added, and stirred at 65°C for 1 h under nitrogen atmosphere. After the mixture was clarified, 0.8 g of 1,3-divinylbenzene was added again, and stirred at 65°C for 12 h again, and the foaming was completed.
[0029] Example 6 In a flask, 0.6 g of dimercaptothiadiazole dimer, 1 g of 2,3-dithio(2-mercapto)-1- propane sulfide, 0.6 g of 1,3-divinylbenzene and 30 mg of 2,2'-azobisisobutyronitrile were added, and stirred at 65°C for 1 h under nitrogen atmosphere. After the mixture was clarified, 0.8 g of 1,3-divinylbenzene was added again, and stirred at 65°C for 12 h again, and the foaming was completed.
[0030] The above-described example 4 is a preferred embodiment of the present application, but the embodiments of the present application are not limited to the above-described example, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application should be equivalent replacement methods, and are all included in the protection scope of the present application.
[0031] Comparative Example 1 In a flask, 0.5 g of dimercaptothiadiazole dimer, 0.5 g of 1,3-diisopropenylbenzene and 30 mg of 2,2'-azobisisobutyronitrile were added, and stirred at 65°C for 1 h under nitrogen atmosphere. Compared with example 4, the dimercaptothiadiazole dimer was not dissolved, and the subsequent process could not be carried out.
[0032] Comparative Example 2 In a flask, 0.5 g of dimercaptothiadiazole dimer, 1 g of 2,3-dithio(2-mercapto)-l- propane thiol, was stirred at 65°C under nitrogen for 1 h. Compared with Example 4, the dimercaptothiadiazole dimer was not dissolved, and the subsequent reaction could not be carried out.
[0033] Comparative Example 3 In a flask, 1 g of 2,3-dithio(2-mercapto)-l-propane thiol, 0.5 g of 1,3-diisopropenylbenzene, and 30 mg of 2,2'-azobis(isobutyronitrile) were stirred at 65°C under nitrogen for 1 h. After the mixture was clarified, 1 g of 1,3-diisopropenylbenzene was added again, and stirring was continued at 65°C for 12 h. Compared with Example 4, the material solidified into a block after the reaction, and did not foam.
[0034] Table 1 is a table of densities of Examples 1-4 in the method of preparing the dimercaptothiadiazole-added polystyrene foaming material according to the present application; Table 1
[0035] Table 2 is a table of foaming rates of Examples 1-4 in the method of preparing the dimercaptothiadiazole-added polystyrene foaming material according to the present application; Table 2
[0036] Table 3 is a table of differences in phenomena between the best example 4 and the comparative examples according to the present application Table 3
[0037] Figure 1 (a) The overhead view of the dimercaptothiadiazole dimer-added polystyrene foaming material shows that the pore structure of the material indicates that the material foamed successfully, and Figure 1 (b), (c) It can be seen that the strain of the material is less than 5% after 6.2 kPa pressure is applied to the surface thereof, showing excellent compressive strength thereof.
[0038] Comparative Example 1, which did not add 2,3-dithio(2-mercapto)-l-propane thiol according to the present application, had the same conditions as Example 4. It can be proved by Comparative Example 1 that the crosslinking agent can assist the dimercaptothiadiazole dimer to participate in the reaction.
[0039] Comparative Example 2, which did not add 1,3-diisopropenylbenzene according to the present application, had the same conditions as Example 4. It can be proved by Comparative Example 2 that the monomer can react with the dimercaptothiadiazole dimer.
[0040] Comparative Example 3, which did not add dimercaptothiadiazole dimer according to the present application, had the same conditions as Example 4. It can be proved by Comparative Example 3 that the raw material participates in and dominates the foaming reaction.
[0041] Example 7 In a flask was added 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithia(2-mercapto)-1-propane sulfide, 0.25 g of 1,3-divinylbenzene and 20 mg of 2,2'-azobisisobutyronitrile and stirred at 55 °C for 30 min under a nitrogen blanket. After the mixture was clear, an additional 0.5 g of 1,3-divinylbenzene was added and stirred at 65 °C for an additional 8 h, at which time the foaming was complete.
[0042] Example 8 In a flask was added 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithia(2-mercapto)-1-propane sulfide, 0.25 g of 1,3-divinylbenzene and 20 mg of 2,2'-azobisisobutyronitrile and stirred at 55 °C for 90 min under a nitrogen blanket. After the mixture was clear, an additional 0.5 g of 1,3-divinylbenzene was added and stirred at 65 °C for an additional 8 h, at which time the foaming was complete.
[0043] Example 9 In a flask was added 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithia(2-mercapto)-1-propane sulfide, 0.25 g of 1,3-divinylbenzene and 20 mg of 2,2'-azobisisobutyronitrile and stirred at 75 °C for 90 min under a nitrogen blanket. After the mixture was clear, an additional 0.5 g of 1,3-divinylbenzene was added and stirred at 65 °C for an additional 8 h, at which time the foaming was complete.
[0044] Example 10 In a flask was added 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithia(2-mercapto)-1-propane sulfide, 0.25 g of 1,3-divinylbenzene and 20 mg of 2,2'-azobisisobutyronitrile and stirred at 55 °C for 60 min under a nitrogen blanket. After the mixture was clear, an additional 0.5 g of 1,3-divinylbenzene was added and stirred at 65 °C for an additional 8 h, at which time the foaming was complete.
[0045] Example 11 In a flask was added 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithia(2-mercapto)-1-propane sulfide, 0.25 g of 1,3-divinylbenzene and 20 mg of 2,2'-azobisisobutyronitrile and stirred at 55 °C for 60 min under a nitrogen blanket. After the mixture was clear, an additional 0.5 g of 1,3-divinylbenzene was added and stirred at 65 °C for an additional 14 h, at which time the foaming was complete.
[0046] Example 12 Add 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithio(2-mercapto)-1-propanesulfonate, 0.25 g of 1,3-divinylbenzene, and 20 mg of 2,2'-azobisisobutyronitrile to a flask, and stir at 55 °C for 60 min under nitrogen atmosphere. After the mixture becomes clear, add another 0.5 g of 1,3-divinylbenzene and stir again at 55 °C for 14 h to complete foaming.
[0047] Example 13 Add 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithio(2-mercapto)-1-propanesulfonate, 0.25 g of 1,3-divinylbenzene, and 20 mg of 2,2'-azobisisobutyronitrile to a flask, and stir at 55 °C for 80 min under nitrogen atmosphere. After the mixture becomes clear, add another 0.5 g of 1,3-divinylbenzene and stir again at 55 °C for 13 h to complete foaming.
[0048] Example 14 Add 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithio(2-mercapto)-1-propanesulfonate, 0.25 g of 1,3-divinylbenzene, and 20 mg of 2,2'-azobisisobutyronitrile to a flask, and stir at 75 °C for 90 min under nitrogen atmosphere. After the mixture becomes clear, add another 0.5 g of 1,3-divinylbenzene and stir again at 55 °C for 12 h to complete foaming.
[0049] Example 15 Add 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithio(2-mercapto)-1-propanesulfonate, 0.25 g of 1,3-divinylbenzene, and 20 mg of 2,2'-azobisisobutyronitrile to a flask, and stir at 65 °C for 85 min under nitrogen atmosphere. After the mixture becomes clear, add another 0.5 g of 1,3-divinylbenzene and stir again at 75 °C for 7 h to complete foaming.
[0050] Example 16 Add 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithio(2-mercapto)-1-propanesulfonate, 0.25 g of 1,3-divinylbenzene, and 20 mg of 2,2'-azobisisobutyronitrile to a flask, and stir at 75 °C for 65 min under nitrogen atmosphere. After the mixture becomes clear, add another 0.5 g of 1,3-divinylbenzene and stir again at 75 °C for 8 h to complete foaming.
[0051] Example 17 Add 0.25 g of dimercaptothiadiazole, 0.5 g of 2,3-dithio(2-mercapto)-1-propanesulfonate, 0.25 g of 1,3-divinylbenzene, and 20 mg of 2,2'-azobisisobutyronitrile to a flask, and stir at 65 °C for 75 min under nitrogen atmosphere. After the mixture becomes clear, add another 0.5 g of 1,3-divinylbenzene and stir again at 75 °C for 11 h to complete foaming.
Claims
1. A method for producing a non-polyurethane-based foamed material, characterized by: Specifically comprising the following steps: Step 1, reacting and dissolving dimercaptothiadiazole materials; Step 2, adding the mixture treated in step 1 into divinylbenzene for polymerization and foaming.
2. The method for producing a non-polyurethane-based foam material according to claim 1, characterized by: The specific process of step 1 is: under the nitrogen environment, dimercaptothiadiazole materials, divinylbenzene, 2,3-dithio(2-mercapto)-1-propane thiol and 2,2'-azobis isobutyronitrile are poured into a flask for stirring.
3. The method for producing a non-polyurethane-based foam material according to claim 2, characterized by: In step 1, the dimercaptothiadiazole material is one of dimercaptothiadiazole or dimercaptothiadiazole dimer.
4. The method for producing a non-polyurethane-based foam material according to claim 2, characterized by: In step 1, the divinylbenzene is one of 1,3-diisopropenylbenzene or 1,3-divinylbenzene.
5. The method for producing a non-polyurethane-based foam material according to claim 2, characterized by: In step 1, the mass ratio of dimercaptothiadiazole material, divinylbenzene and 2,3-dithio(2-mercapto)-1-propane thiol is 0.8-1.2:0.8:1.2:1.8-2.
2.
6. The method for producing a non-polyurethane-based foam material according to claim 2, characterized by: In step 1, the stirring temperature is 50-80℃, and the stirring time is 30-90min.
7. The method for producing a non-polyurethane-based foam material according to claim 2, characterized by: The specific process of step 2 is: the mixture after step 1 reaction is added into divinylbenzene again under the nitrogen atmosphere, and the stirring is continued.
8. The method for producing a non-polyurethane-based foam material according to claim 7, characterized by: In step 2, the mass ratio of step 1 product and divinylbenzene is 2:0.8-1.
2.
9. The method for producing a non-polyurethane-based foam material according to claim 8, characterized by: In step 2, the stirring temperature is 50-80℃, and the stirring time is 6-14h.
10. A non-polyurethane foaming material prepared by the method of any one of claims 1-9.