CN111116864B - Preparation method and product of polyurethane foam plastic capable of being thermoplastically processed - Google Patents
Preparation method and product of polyurethane foam plastic capable of being thermoplastically processed Download PDFInfo
- Publication number
- CN111116864B CN111116864B CN201911349211.5A CN201911349211A CN111116864B CN 111116864 B CN111116864 B CN 111116864B CN 201911349211 A CN201911349211 A CN 201911349211A CN 111116864 B CN111116864 B CN 111116864B
- Authority
- CN
- China
- Prior art keywords
- polyurethane foam
- plastic
- polyether polyol
- dynamic covalent
- polyurethane
- 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
Images
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
- 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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- 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
- C08G18/4825—Polyethers containing two 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
- C08G18/28—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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6453—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a preparation method of thermoplastically processable polyurethane foam plastic and a product, belonging to the technical field of high polymer materials. The method comprises the following steps: polyether polyol, dynamic covalent compound, catalyst, water and silicone oil are mixed uniformly at room temperature, added with toluene diisocyanate, mixed uniformly again and kept stand for foaming for 4-24h to prepare the thermoplastically processable polyurethane foam plastic. The foamed plastic has the appearance, density and mechanical property similar to those of the traditional polyurethane foamed plastic, can be subjected to thermoplastic processing at the temperature of 160-190 ℃ to obtain plastic capable of being repeatedly processed, and the mechanical property of the plastic cannot be reduced after the repeated processing. After the foamed plastic is discarded, the foamed plastic can be processed and molded through simple and direct heating and plasticizing, a new regenerated polyurethane material with excellent performance is obtained, the sustainable development of the polyurethane foamed plastic can be promoted, and greater economic benefit and environmental benefit are created. The method is simple and easy to operate, does not need special instruments and equipment, has strong operability and is suitable for expanded production.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method and a product of thermoplastically processable polyurethane foam plastic.
Background
Polyurethane foam is widely applied, and particularly becomes one of indispensable materials in the fields of furniture, household appliances, buildings, transportation, heat insulation, heat preservation, automobile interior decoration and the like. At present, China becomes the world with the largest capacity and consumption of polyurethane foam plastics, and the accumulation of a large amount of waste polyurethane foam plastics causes serious environmental pollution and resource waste. Therefore, recycling of waste polyurethane foams has become increasingly urgent and has important environmental and economic benefits. However, polyurethane foam is a three-dimensional network cross-linked thermosetting material, cannot be melted and is insoluble, which causes great difficulty in recycling.
At present, three main methods for recycling and treating waste polyurethane foam plastics are provided: physical recovery methods, chemical recovery methods, and energy recovery methods. The physical recovery method is to wash, dry and crush the waste polyurethane foam plastics, then mix the waste polyurethane foam plastics as a filler with an adhesive or thermoplastic plastics, and realize recycling through hot-press molding or extrusion molding. The chemical recovery method is to degrade waste polyurethane foam plastics into low molecular weight chemicals under the action of a chemical degradation agent, and although the method can obtain high-quality products, the method generally has the defects of complex process, poor environmental protection, low cost performance and the like. The energy recovery method is a method for obtaining energy by mixing and burning waste polyurethane foam and other waste plastics or coal, and although the method can reduce the problem of accumulation of the waste polyurethane foam, the polyurethane foam contains a large amount of nitrogen elements, benzene rings and the like, and the combustion can cause the emission of a large amount of toxic and harmful gases, thereby causing serious atmospheric pollution.
Therefore, although there are many methods for recycling waste polyurethane foam, these methods have more or less defects, and it is difficult to achieve efficient, low-cost and low-pollution recycling of waste polyurethane foam. If the polyurethane foam plastic capable of being processed by thermoplastic processing can be prepared from a chemical structure, the polyurethane foam plastic can be processed and molded after being discarded through simple and direct heating and plasticizing, and a new regenerated polyurethane material with excellent performance is obtained, the sustainable development of the polyurethane foam plastic can be promoted, and greater economic benefit and environmental benefit can be created.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a process for the preparation of thermoplastically processable polyurethane foams; the second object is to provide a thermoplastically processable polyurethane foam.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a process for the preparation of a thermoplastically processable polyurethane foam, which process comprises:
polyether polyol, dynamic covalent compound, catalyst, water and silicone oil are mixed uniformly at room temperature, toluene diisocyanate is added, and the mixture is mixed uniformly again and then is kept stand for foaming to prepare the thermoplastically processable polyurethane foam plastic.
Preferably, the mass ratio of the dynamic covalent compound to the polyether polyol is 5-40: 100; the mass of the catalyst is 0.1-1.2% of the total mass of the polyether polyol and the dynamic covalent compound; the mass of the water is 2-4% of the total mass of the polyether polyol and the dynamic covalent compound; the mass of the silicone oil is 0.5-2% of the total mass of the polyether polyol and the dynamic covalent compound; the molar ratio of isocyanate groups in the toluene diisocyanate to the sum of hydroxyl groups in the polyether polyol and amino groups in the dynamic covalent compound is 1.05-1.25: 1.
Preferably, the polyether polyol is polypropylene glycol.
Preferably, the hydroxyl value of the polypropylene glycol is 56.
Preferably, the dynamic covalent compound is one of dithiodiethylene glycol, dithiodiphenylamine, dithiobenzhydrol or liquid polysulfide rubber.
Preferably, the catalyst is a mixture formed by mixing triethylene diamine A33 and stannous octoate T9 according to the mass ratio of 2:1-1: 2.
Preferably, the foaming time is 4-24 h.
2. Thermoplastically processable polyurethane foams are prepared by the process.
The invention has the beneficial effects that: the invention provides a preparation method and a product of thermoplastically processed polyurethane foam plastic, wherein a specific dynamic covalent compound is added in the process of preparing the polyurethane foam plastic, so as to overcome the defects that the reaction speed of the dynamic covalent compound and the reaction speed of polyether polyol are not matched with that of isocyanate to cause unsuccessful foaming and no polyurethane foam plastic is obtained or the prepared foam plastic can generate serious volume shrinkage and no high-quality polyurethane foam plastic is obtained due to different reactive functional groups of the dynamic covalent compound and hydroxyl of the polyether polyol; and further controlling the mass ratio of the dynamic covalent compound to the polyether polyol to further ensure that a high-quality thermoplastically processable polyurethane foam can be prepared, because the dynamic covalent compound is a small-molecular compound with a molecular weight much smaller than that of the polyether polyol, when the content of the dynamic covalent compound is too large, foaming difficulty is increased, an ideal foaming material cannot be obtained, and when the content of the dynamic covalent compound is too small, covalent bonds capable of undergoing an exchange reaction are too few, and the polyurethane foam is still dominated by a permanent crosslinking structure and is not enough to endow the polyurethane foam with plastic processability. The polyurethane foam plastic prepared by the method has similar appearance, density and mechanical property to the traditional polyurethane foam plastic, can be processed by hot molding at the temperature of 160-190 ℃ to obtain plastic which can be processed repeatedly, and the mechanical property of the plastic can not be reduced after repeated processing. After the polyurethane foam plastic capable of being thermoplastically processed is abandoned, the polyurethane foam plastic can be processed and molded through simple and direct heating and plasticizing, a new regenerated polyurethane material with excellent performance is obtained, the sustainable development of the polyurethane foam plastic can be promoted, and greater economic benefit and environmental benefit are created. The method is simple and easy to operate, does not need special instruments and equipment, has strong operability and is suitable for expanded production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a topographic map of a thermoplastically processable polyurethane foam prepared in example 5 before and after hot pressing (a in FIG. 1 is a topographic map of the polyurethane foam before hot pressing, and b in FIG. 1 is a topographic map of the polyurethane foam after hot pressing);
FIG. 2 is a profile before and after hot-pressing of the polyurethane foam prepared in the comparative example (a in FIG. 2 is a profile before hot-pressing of the polyurethane foam, and b in FIG. 2 is a profile after hot-pressing of the polyurethane foam).
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparation of thermoplastically processable polyurethane foams
100 parts of polypropylene glycol with hydroxyl value of 56, 5 parts of dithio diphenylamine, 0.05 part of triethylene diamine A33, 0.055 part of stannous octoate T9, 2.1 parts of water and 0.525 part of silicone oil are added into a reactor, the mixture is stirred and mixed uniformly at room temperature, then toluene diisocyanate is added according to the molar ratio of isocyanate group in the toluene diisocyanate to the sum of hydroxyl group in the polypropylene glycol and amino group in the dithio diphenylamine, the mixture is stirred and mixed uniformly and quickly, and then the mixture is kept stand and foamed for 4 hours to prepare the polyurethane foam plastic capable of being processed by thermoplasticity.
The polyurethane foam had a density of 32kg/m3The tensile strength is 160 +/-13 kPa,the elongation at break was 275. + -. 8%.
Preheating the polyurethane foam plastic in a flat vulcanizing machine at 160 ℃ for 10min, and then carrying out hot pressing under the pressure of 10MPa for 10min to obtain the polyurethane plastic, wherein the tensile strength of the polyurethane plastic is 10.3 +/-0.2 MPa, and the elongation at break is 130 +/-5%; the polyurethane plastic after thermoplastic processing is processed again under the same condition, the tensile strength is 10.7 plus or minus 0.2MPa, and the elongation at break is 127 plus or minus 9 percent.
Example 2
Preparation of thermoplastically processable polyurethane foams
100 parts of polypropylene glycol with a hydroxyl value of 56, 10 parts of dithiodiethylene glycol, 0.4 part of triethylene diamine A33, 0.2 part of stannous octoate T9, 3 parts of water and 1 part of silicone oil are added into a reactor, the mixture is stirred and mixed uniformly at room temperature, then toluene diisocyanate is added according to the molar ratio of isocyanate groups in the toluene diisocyanate to the sum of hydroxyl groups in the polypropylene glycol and amino groups in the dithiodiphenylamine being 1.1:1, the mixture is quickly stirred and mixed uniformly, and then the mixture is kept stand and foamed for 8 hours to prepare the thermoplastically processable polyurethane foam plastic.
The polyurethane foam had a density of 35kg/m3The tensile strength was 148. + -. 9kPa, and the elongation at break was 297. + -. 11%.
Preheating the polyurethane foam plastic in a flat vulcanizing machine at 170 ℃ for 10min, and then carrying out hot pressing under the pressure of 10MPa for 10min to obtain the polyurethane plastic, wherein the tensile strength of the polyurethane plastic is 12.3 +/-0.5 MPa, and the elongation at break is 198 +/-13%; the polyurethane plastic after thermoplastic processing is processed again under the same condition, the tensile strength is 11.9 plus or minus 0.2MPa, and the elongation at break is 203 plus or minus 9 percent.
Example 3
Preparation of thermoplastically processable polyurethane foams
100 parts of polypropylene glycol with a hydroxyl value of 56, 20 parts of dithio-benzhydryl alcohol, 0.4 part of triethylene diamine A33, 0.8 part of stannous octoate T9, 4 parts of water and 2 parts of silicone oil are added into a reactor, after stirring and uniformly mixing at room temperature, toluene diisocyanate is added according to the molar ratio of isocyanate groups in the toluene diisocyanate to the sum of hydroxyl groups in the polypropylene glycol and amino groups in the dithio-diphenylamine in a ratio of 1.2:1, and after rapid stirring and uniform mixing, standing and foaming are carried out for 24 hours, thus obtaining the thermoplastically processable polyurethane foam plastic.
The polyurethane foam had a density of 41kg/m3The tensile strength is 164 +/-9 kPa, and the breaking elongation is 265 +/-13%.
Preheating the polyurethane foam plastic in a flat vulcanizing machine at 180 ℃ for 10min, and then carrying out hot pressing under the pressure of 10MPa for 10min to obtain the polyurethane plastic, wherein the tensile strength of the polyurethane plastic is 18.7 +/-0.9 MPa, and the elongation at break is 189 +/-6%; the polyurethane plastic after thermoplastic processing is processed again under the same conditions, the tensile strength is 18.4 +/-0.5 MPa, and the elongation at break is 193 +/-8%.
Example 4
Preparation of thermoplastically processable polyurethane foams
100 parts of polypropylene glycol with a hydroxyl value of 56, 30 parts of dithiodiethylene glycol, 0.5 part of triethylene diamine A33, 0.5 part of stannous octoate T9, 3 parts of water and 1 part of silicone oil are added into a reactor, the mixture is stirred and mixed uniformly at room temperature, then toluene diisocyanate is added according to the molar ratio of isocyanate groups in the toluene diisocyanate to the sum of hydroxyl groups in the polypropylene glycol and amino groups in the dithio diphenylamine, the mixture is quickly stirred and mixed uniformly, and then the mixture is kept stand and foamed for 18 hours to prepare the thermoplastically-processable polyurethane foam plastic.
The polyurethane foam had a density of 37kg/m3, a tensile strength of 173. + -. 9kPa, and an elongation at break of 258. + -. 15%.
Preheating the polyurethane foam plastic in a flat vulcanizing machine at 180 ℃ for 10min, and then carrying out hot pressing under the pressure of 10MPa for 10min to obtain the polyurethane plastic, wherein the tensile strength of the polyurethane plastic is 20.3 +/-0.8 MPa, and the elongation at break is 176 +/-7%; the polyurethane plastic after thermoplastic processing is processed again under the same condition, the tensile strength is 20.4 plus or minus 0.7MPa, and the elongation at break is 178 plus or minus 8 percent.
Example 5
Preparation of thermoplastically processable polyurethane foams
100 parts of polypropylene glycol with the hydroxyl value of 56, 40 parts of liquid polysulfide rubber, 0.1 part of triethylene diamine A33, 0.2 part of stannous octoate T9, 3 parts of water and 1 part of silicone oil are added into a reactor, the mixture is stirred and mixed uniformly at room temperature, then toluene diisocyanate is added according to the molar ratio of isocyanate groups in the toluene diisocyanate to the sum of hydroxyl groups in the polypropylene glycol and amino groups in the dithio diphenylamine, the mixture is quickly stirred and mixed uniformly, and then the mixture is kept stand and foamed for 24 hours to prepare the thermoplastically processed polyurethane foam plastic.
The polyurethane foam had a density of 38kg/m3The tensile strength is 167 +/-11 kPa, and the elongation at break is 293 +/-8%.
Preheating the polyurethane foam plastic in a flat vulcanizing machine at 180 ℃ for 10min, and then carrying out hot pressing under the pressure of 10MPa for 10min to obtain the polyurethane plastic, wherein the tensile strength of the polyurethane plastic is 13.9 +/-0.7 MPa, and the elongation at break is 93 +/-8%; the polyurethane plastic after thermoplastic processing is processed again under the same condition, the tensile strength is 13.5 plus or minus 0.2MPa, and the elongation at break is 95 plus or minus 7 percent.
Comparative examples
The difference from example 5 is that a polyurethane foam was obtained without adding 40 parts of the liquid polysulfide rubber.
The polyurethane foam has a density of 33kg/m3The tensile strength is 178 +/-14 kPa, and the breaking elongation is 293 +/-8%.
The polyurethane foam plastic is preheated in a flat vulcanizing machine at 180 ℃ for 10min and then hot-pressed under the pressure of 10MPa for 10min, so that the plastic cannot be obtained.
FIG. 1 is a view of the morphology of a thermoplastically processable polyurethane foam prepared in example 5 before and after hot pressing, wherein a in FIG. 1 is a view of the morphology of the polyurethane foam before hot pressing, and b in FIG. 1 is a view of the morphology of the polyurethane foam after hot pressing.
FIG. 2 is a profile before and after hot pressing of a polyurethane foam prepared in a comparative example, wherein a in FIG. 2 is a profile before hot pressing of the polyurethane foam, and b in FIG. 2 is a profile after hot pressing of the polyurethane foam.
As can be seen from a comparison of FIGS. 1 and 2, the polyurethane foam containing no dynamic covalent bonds in the comparative example has no thermoplastic processability and, although it was able to be collapsed by heating, the foam blocks could not be fused together, whereas the polyurethane foam containing dynamic covalent bonds in example 5 was able to obtain a complete polyurethane after hot pressing.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (4)
1. A process for the preparation of thermoplastically processable polyurethane foams, characterized in that it comprises the following steps: polyether polyol, dynamic covalent compound, catalyst, water and silicone oil are mixed uniformly at room temperature, toluene diisocyanate is added, and the mixture is mixed uniformly again and then is kept stand for foaming to prepare thermoplastically processable polyurethane foam plastic;
the mass ratio of the dynamic covalent compound to the polyether polyol is 5-40: 100; the mass of the catalyst is 0.1-1.2% of the total mass of the polyether polyol and the dynamic covalent compound; the mass of the water is 2-4% of the total mass of the polyether polyol and the dynamic covalent compound; the mass of the silicone oil is 0.5-2% of the total mass of the polyether polyol and the dynamic covalent compound; the molar ratio of isocyanate groups in the toluene diisocyanate to the sum of hydroxyl groups in the polyether polyol and reactive functional groups in the dynamic covalent compound that react with the isocyanate groups is 1.05-1.25: 1;
the dynamic covalent compound is one of dithiodiglycol, dithiodiphenylamine, dithiobenzhydrol or liquid polysulfide rubber;
the catalyst is a mixture formed by mixing triethylene diamine A33 and stannous octoate T9 according to the mass ratio of 2:1-1: 2;
the polyether polyol is polypropylene glycol.
2. The method of claim 1, wherein said polypropylene glycol has a hydroxyl number of 56.
3. The method of claim 1, wherein the foaming time is from 4 to 24 hours.
4. Thermoplastically processable polyurethane foams prepared by the process of any of claims 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911349211.5A CN111116864B (en) | 2019-12-24 | 2019-12-24 | Preparation method and product of polyurethane foam plastic capable of being thermoplastically processed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911349211.5A CN111116864B (en) | 2019-12-24 | 2019-12-24 | Preparation method and product of polyurethane foam plastic capable of being thermoplastically processed |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111116864A CN111116864A (en) | 2020-05-08 |
| CN111116864B true CN111116864B (en) | 2022-06-10 |
Family
ID=70500511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911349211.5A Active CN111116864B (en) | 2019-12-24 | 2019-12-24 | Preparation method and product of polyurethane foam plastic capable of being thermoplastically processed |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111116864B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376718A (en) * | 2008-08-13 | 2009-03-04 | 刘建平 | Method for recycling waste polyurethane |
| CN101563394A (en) * | 2006-12-20 | 2009-10-21 | 米其林技术公司 | Polyurethane |
| CN101629025A (en) * | 2009-08-07 | 2010-01-20 | 天津大学 | Plastic material prepared by using waste thermosetting foam plastics and preparation method thereof |
| CN102807730A (en) * | 2012-07-25 | 2012-12-05 | 浙江吉利汽车研究院有限公司杭州分公司 | Method for recovering rigid polyurethane foam plastic |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1034482A (en) * | 1963-01-11 | 1966-06-29 | Lankro Chem Ltd | Improvements in or relating to polyethers and polyurethanes obtained therefrom |
| US3337487A (en) * | 1963-07-29 | 1967-08-22 | Hercules Inc | Reactive end-group polymers and preparation thereof |
| US20020156333A1 (en) * | 2001-02-02 | 2002-10-24 | Oren Rosen | Instant degradation of plastics into soluble non-toxic products |
| KR20160118977A (en) * | 2015-04-01 | 2016-10-12 | 주식회사 삼양사 | Method of using self-healable polyurethane and self-healable composition |
| CN106397755A (en) * | 2015-08-02 | 2017-02-15 | 青岛科技大学 | Preparation method for polyester polyol containing disulfide bond |
| CN105801796A (en) * | 2016-04-25 | 2016-07-27 | 苏州亚科塑胶有限公司 | Preparation method of ultra-soft polyurethane foam plastics |
| CN107805308B (en) * | 2016-09-09 | 2022-04-15 | 翁秋梅 | Dynamic polymer with hybrid cross-linked network and application thereof |
| CN107602790A (en) * | 2017-10-26 | 2018-01-19 | 西南大学 | A kind of high-performance and can reprocessabilty castor oil network polymer and preparation method thereof |
| CN109232847B (en) * | 2018-09-27 | 2021-08-10 | 湖南科旺科技有限公司 | Flame-retardant polyurethane foam plastic and preparation method thereof |
| CN109881301B (en) * | 2019-03-05 | 2021-04-20 | 华峰化学股份有限公司 | Preparation method of room-temperature self-repairing polyurethane elastic fiber |
| CN110452367B (en) * | 2019-08-07 | 2021-09-14 | 西南大学 | Preparation method of aliphatic polyester dynamic covalent network polymer and product thereof |
-
2019
- 2019-12-24 CN CN201911349211.5A patent/CN111116864B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101563394A (en) * | 2006-12-20 | 2009-10-21 | 米其林技术公司 | Polyurethane |
| CN101376718A (en) * | 2008-08-13 | 2009-03-04 | 刘建平 | Method for recycling waste polyurethane |
| CN101629025A (en) * | 2009-08-07 | 2010-01-20 | 天津大学 | Plastic material prepared by using waste thermosetting foam plastics and preparation method thereof |
| CN102807730A (en) * | 2012-07-25 | 2012-12-05 | 浙江吉利汽车研究院有限公司杭州分公司 | Method for recovering rigid polyurethane foam plastic |
Non-Patent Citations (4)
| Title |
|---|
| Malleable and thermally recyclable polyurethane foam;Xiang-Zhao Wang等;《GREEN CHEMISTRY》;20201211;第23卷;第307-313页 * |
| 废旧硬质聚氨酯泡沫塑料的回收处理技术现状;牟善友等;《山东化工》;20170923(第18期);第208-209页 * |
| 捕集重金属的DTC改性聚氨酯泡沫研究;李健等;《聚氨酯工业》;20170228(第01期);第34-37页 * |
| 聚氨酯废旧料的回收利用;刘益军等;《化工科技市场》;19990930(第09期);第14-17页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111116864A (en) | 2020-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020125577A1 (en) | Biodegradable thermoplastic polyurethane elastomer foam beads and preparation method therefor | |
| CN108047423B (en) | Environment-friendly polyurethane football toy composition and preparation method thereof | |
| CN110922564A (en) | Polyether ester type thermoplastic polyurethane elastomer foaming bead and preparation method thereof | |
| CN112708163A (en) | Preparation method of high-resilience biodegradable polyester micro-foaming profiled bar | |
| CN108948410B (en) | Polyol composition and polyurethane rigid foam prepared from same | |
| CN110964173B (en) | Polyurethane composition for honeycomb composite material, preparation method of polyurethane composition, polyurethane foam and application of polyurethane foam | |
| CN106883591B (en) | Method for utilizing polyurethane waste material and elastomer | |
| CN104448745A (en) | Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) foaming material and preparation method thereof | |
| CN110041501B (en) | Polyurethane latex flexible foam for mattress and preparation method thereof | |
| CN111116864B (en) | Preparation method and product of polyurethane foam plastic capable of being thermoplastically processed | |
| CN101624452A (en) | Method for producing thermoplastic urethane foam | |
| CN102604347A (en) | Preparation method of chitosan modified polylactic acid material by gamma-ray irradiation | |
| CN111607062B (en) | Biomass polyurethane foam material and preparation method thereof | |
| CN107298748B (en) | Environment-friendly degradable flame-retardant polyurethane rapid packaging material and preparation method thereof | |
| CN102617969B (en) | Preparation method of thermoplastic konjac glucomannan/poly butylenes succinate blending material | |
| CN103525077A (en) | Surface oxidation modified vulcanized rubber powder/polyurethane composite material and preparation method thereof | |
| CN111704755A (en) | Preparation method of rubber foam material with bubble inner wall shell | |
| CN114456344A (en) | Low-carbon environment-friendly full-bio-based semi-rigid polyurethane foam formula | |
| CN104497343A (en) | Preparation method of polymethacrylimide micro-foaming material and product thereof | |
| CN114716641A (en) | Polyurethane foam composition and preparation method thereof | |
| CN109749306B (en) | Porous foam material and preparation method thereof | |
| CN113980454A (en) | Ultralow-density polyurethane mid-sole or insole composite material containing recyclable waste particles and preparation method thereof | |
| CN102391518A (en) | Polyurethane modified phenolic resin, preparation method thereof and phenolic resin molding powder composition | |
| CN115073799B (en) | Preparation method of expandable poly (butylene succinate) | |
| CN112552631A (en) | Degradable pearl cotton and low-temperature degradation treatment process 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 |