CN110643011B - High-strength polyurethane foam composition, polyurethane foam and synthesis method thereof - Google Patents
High-strength polyurethane foam composition, polyurethane foam and synthesis method thereof Download PDFInfo
- Publication number
- CN110643011B CN110643011B CN201910709898.2A CN201910709898A CN110643011B CN 110643011 B CN110643011 B CN 110643011B CN 201910709898 A CN201910709898 A CN 201910709898A CN 110643011 B CN110643011 B CN 110643011B
- Authority
- CN
- China
- Prior art keywords
- polyurethane foam
- component
- strength polyurethane
- temperature
- parts
- 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
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/184—Binary blends of expanding agents of chemical foaming agent and physical blowing agent, e.g. azodicarbonamide and fluorocarbon
-
- 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
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a high-strength polyurethane foam composition, which comprises a component A and a component B, wherein the component A comprises polyester polyol, silicone oil, a first catalyst, a flame retardant and a foaming agent, and the component B is isocyanate, wherein the polyester polyol is prepared from the following raw materials in parts by weight: 90-100 parts of phthalic anhydride; 25-35 parts of terephthalic acid; 25-35 parts of adipic acid; 80-90 parts of glycerol; 130-150 parts of diethylene glycol; 40-60 parts of unsaturated fatty acid; 0.1-1 part of a second catalyst; 5-10 parts of trimethylolpropane. The invention also relates to high-strength polyurethane foam and a preparation method thereof. Compared with the prior art, the polyurethane foam prepared by the invention has the advantages of high compressive strength and good flame retardant property.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a high-strength polyurethane foam composition, polyurethane foam and a synthesis method thereof.
Background
Polyurethane resin is short for polyurethane and is a high molecular material. Polyurethane is a new organic polymer material, is known as 'fifth plastic', and has the advantages of foamability, elasticity, wear resistance, adhesion, low temperature resistance, solvent resistance, biological aging resistance and the like, so that the polyurethane has wide application, is developed quickly in recent years, and forms a larger production scale in the polyurethane industry.
However, the strength of polyurethane foam is relatively poor, and in order to improve the strength of polyurethane foam, it is generally necessary to add some high-strength particles or nano-powders to polyurethane foam, the former adversely affects the uniformity of polyurethane foam, and the latter increases the cost of polyurethane foam more. Therefore, it is necessary to find a high-strength polyurethane foam.
Disclosure of Invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art by providing a composition for producing a high-strength polyurethane foam.
It is also an object of the present invention to provide a process for the preparation of a high strength polyurethane foam and a high strength polyurethane foam prepared by the above process.
In order to achieve the object of the present invention, the present application provides the following technical solutions.
In a first aspect, the present application provides a high strength polyurethane foam composition comprising an a-side and a B-side, the a-side comprising the following parts by weight:
the component B is isocyanate; the mass ratio of the component A to the component B is 1: 1.5-2;
the polyester polyol is prepared from the following raw materials in parts by weight:
in a preferable embodiment of the first aspect, the second catalyst includes dibutyltin dilaurate and tetrabutyl titanate, and a mass ratio of the dibutyltin dilaurate to the tetrabutyl titanate is 1-2: 1.
In a preferred version of the first aspect, the first catalyst comprises one or more of PC-5, PC-8 or potassium isooctanoate.
In a preferred version of the first aspect, the flame retardant comprises tris- (2-chloropropyl) phosphate.
In a preferred version of the first aspect, the blowing agent comprises a physical blowing agent comprising HCFC-141b and a chemical blowing agent comprising water.
In a preferred version of the first aspect, the isocyanate comprises one of PM200 (warfarin chemical), 44V20 (kochu) or M20S (basf).
In a second aspect, the present application provides a method for preparing a high-strength polyurethane foam using the above composition, the method comprising the steps of:
(1) mixing the phthalic anhydride, the terephthalic acid, the adipic acid, the glycerol, the diethylene glycol, the unsaturated fatty acid, the second catalyst and the trimethylolpropane according to a ratio, placing the mixture in an inert gas atmosphere, carrying out heating reaction in stages, and after the reaction is finished, vacuumizing to prepare the polyester polyol;
(2) uniformly mixing the polyester polyol, the silicone oil, the first catalyst, the foaming agent and the flame retardant in proportion to obtain a component A;
(3) and uniformly mixing the component A and the component B in proportion, and foaming to obtain the high-strength polyurethane foam.
In a preferred embodiment of the second aspect, in step (1), the staged heating reaction specifically includes: reacting for 1.5-3 h at the temperature of 150-160 ℃; reacting for 3-5 h at the temperature of 180-200 ℃; reacting for 5-8 h at the temperature of 200-230 ℃; and/or the inert gas atmosphere is nitrogen atmosphere; and the vacuumizing time is 2-3 h.
In a preferable embodiment of the second aspect, the mixing temperature of step (2) and step (3) is 10 to 35 ℃; the foaming temperature in the step (3) is 10-35 ℃.
In a third aspect, the present application provides a high strength polyurethane foam prepared by the above method.
Compared with the prior art, the invention has the beneficial effects that: the polyurethane foam prepared by the invention has the advantages of high compressive strength and good flame retardant property.
Detailed Description
Unless otherwise defined, technical or scientific terms used herein in the specification and claims should have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All numerical values recited herein as between the lowest value and the highest value are intended to mean all values between the lowest value and the highest value in increments of one unit when there is more than two units difference between the lowest value and the highest value.
While specific embodiments of the invention will be described below, it should be noted that in the course of the detailed description of these embodiments, for the sake of brevity, this specification may not necessarily describe every feature of the actual embodiments in detail. Modifications and substitutions to the embodiments of the present invention may be made by those skilled in the art without departing from the spirit and scope of the present invention, and the resulting embodiments are within the scope of the present invention.
Conventional polyurethane foams have low strength. The object of the present application is to provide a polyurethane foam having high functionality and high strength. The polyurethane foam was prepared from the following composition. The composition comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:
the component B is isocyanate; the mass ratio of the component A to the component B is 1: 1.5-2;
the polyester polyol is prepared from the following raw materials in parts by weight:
in one embodiment, phthalic anhydride is selected from Suiyang technology group, Inc. or Changzhou Qinghong chemical company, Inc., and has a purity of 99.5% or more and a benzoic acid content of 0.05% or less.
In one embodiment, the terephthalic acid may be selected from Nanjing and Seda chemical company Limited, which has a purity of 99% or more.
In one embodiment, the adipic acid may be selected from Nantong Runfeng petrochemical Co., Ltd, and the adipic acid is added into the system, so that the viscosity of the product can be effectively reduced.
In one specific embodiment, glycerol can be selected from Guangzhou Chenghao chemical products, diethylene glycol can be selected from Shanghai petrochemical products, trimethylolpropane can be selected from Wuhanneng medicinal chemical products, and diethylene glycol, trimethylolpropane and glycerol are used together, so that the functionality of the product can be improved, and the viscosity of the product can be reduced.
In one embodiment, the unsaturated fatty acid is preferably a short or medium chain unsaturated fatty acid, which is effective in reducing the viscosity of the product and coordinating the functionality of the product. In one embodiment, the unsaturated fatty acid may be one or more of erucic acid, eleostearic acid, ricinoleic acid and oleic acid.
In a preferable embodiment of the first aspect, the second catalyst includes dibutyltin dilaurate and tetrabutyl titanate, and a mass ratio of the dibutyltin dilaurate to the tetrabutyl titanate is 1-2: 1. The dibutyltin dilaurate is T-12 type.
In a preferred version of the first aspect, the first catalyst comprises one or more of PC-5, PC-8 or potassium isooctanoate. Preferably, the PC-5 is NT CAT PC-5 sold by the Xindian chemical materials (Shanghai) Co., Ltd, the PC-8 is an air chemical product sold, and the potassium isooctanoate (K-15) is sold by the Xindian chemical materials (Shanghai) Co., Ltd. More preferably, the mass ratio of PC-5, PC-8 and K-15 in the first catalyst is 3:8: 15.
In a preferred version of the first aspect, the flame retardant comprises tris- (2-chloropropyl) phosphate. Preferably, the tris- (2-chloropropyl) phosphate (TCPP) is a product sold by Qingdao union industry, and a flame retardant is added, so that the flame retardant property of the polyurethane foam can be effectively improved.
In a preferred version of the first aspect, the blowing agent comprises a physical blowing agent comprising HCFC-141b and a chemical blowing agent comprising water. Preferably, HCFC-141b is selected from Zhejiang Sanjianggong, and water is selected from deionized water. More preferably, the mass ratio of HCFC-141b to water is 20-30: 1.
In a preferred version of the first aspect, the isocyanate comprises one of PM200 (warfarin chemical), 44V20 (kochu) or M20S (basf). Preferably, the polymethylene polyphenyl isocyanate is PM-200 sold by Vanhua chemical group GmbH or MR-200 sold by NPU of Japan, and M20S is Basff.
In a second aspect, the present application provides a method for preparing a high-strength polyurethane foam using the above composition, the method comprising the steps of:
(1) mixing the phthalic anhydride, the terephthalic acid, the adipic acid, the glycerol, the diethylene glycol, the fatty acid, the second catalyst and the trimethylolpropane according to a ratio, placing the mixture in an inert gas atmosphere, carrying out heating reaction in stages, and after the reaction is finished, vacuumizing to prepare the polyester polyol;
(2) uniformly mixing the polyester polyol, the silicone oil, the first catalyst, the foaming agent and the flame retardant in proportion to obtain a component A;
(3) and uniformly mixing the component A and the component B in proportion, and foaming to obtain the high-strength polyurethane foam.
In a preferred embodiment of the second aspect, in step (1), the staged heating reaction specifically includes: reacting for 1.5-3 h at the temperature of 160-170 ℃; reacting for 3-5 h at the temperature of 180-220 ℃; reacting for 5-8 h at 220-230 ℃; and/or the inert gas atmosphere is nitrogen atmosphere; the vacuumizing time is 2-3 h, and the vacuumizing pressure is less than or equal to 0.1 KPa.
In a preferable embodiment of the second aspect, the mixing temperature of step (2) and step (3) is 10 to 35 ℃; the foaming temperature in the step (3) is 20-25 ℃.
In a third aspect, the present application provides a high strength polyurethane foam prepared by the above method.
Examples
The following will describe in detail the embodiments of the present invention, which are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
Example 1
A preparation method of high-functionality polyester polyol comprises the following steps:
(1) weighing 920kg of phthalic anhydride, 300kg of terephthalic acid, 300kg of adipic acid, 810kg of glycerol, 1400kg of diethylene glycol, 500kg of ricinoleic acid, 2kg of dibutyltin dilaurate, 1kg of tetrabutyl titanate and 90kg of trimethylolpropane, and uniformly mixing;
(2) the uniformly mixed raw materials are placed in a reactor, nitrogen is introduced, the mixture is stirred, the mixture reacts for 2 hours at the temperature of 165 ℃, then the mixture is heated to 220 ℃, the mixture reacts for 4 hours at the temperature, then the mixture is heated to 230 ℃, and the mixture reacts for 6 hours at the temperature.
(3) And (3) reducing the temperature in the reactor to 200-210 ℃, and vacuumizing for 2.5h under the pressure of-0.1 MPa to obtain the high-functionality polyester polyol A.
A preparation method of high-strength polyurethane foam comprises the following steps:
(1) taking 100kg of polyester polyol A, and then uniformly mixing with 2.5kg of silicone oil, 0.7kg of deionized water, 0.3kg of PC-5, 0.8kg of PC-8, 1.5kg of K-15, 25kg of HCFC-141b and 15kg of TCPP at 25 ℃ to obtain a component A;
(2) the component A was mixed with 218.7kg of MR-200 at 25 ℃ and foamed at 25 ℃ to prepare a polyurethane foam A.
Example 2
A preparation method of high-functionality polyester polyol comprises the following steps:
(1) weighing 1000kg of phthalic anhydride, 250kg of terephthalic acid, 300kg of adipic acid, 900kg of glycerol, 1300kg of diethylene glycol, 500kg of ricinoleic acid, 2kg of dibutyltin dilaurate, 1kg of tetrabutyl titanate and 90kg of trimethylolpropane, and uniformly mixing;
(2) the uniformly mixed raw materials are placed in a reactor, nitrogen is introduced, the mixture is stirred, the mixture reacts for 2 hours at the temperature of 165 ℃, then the mixture is heated to 220 ℃, the mixture reacts for 4 hours at the temperature, then the mixture is heated to 230 ℃, and the mixture reacts for 6 hours at the temperature.
(3) And (3) reducing the temperature in the reactor to 200-210 ℃, and vacuumizing for 2.5h under the pressure of-0.1 MPa to obtain the high-functionality polyester polyol B.
A preparation method of high-strength polyurethane foam comprises the following steps:
(1) taking 100kg of polyester polyol B, and then uniformly mixing with 2.5kg of silicone oil, 0.7kg of deionized water, 0.3kg of PC-5, 0.8kg of PC-8, 1.5kg of K-15, 25kg of HCFC-141B and 15kg of TCPP at the temperature of 25 ℃ to obtain a component A;
(2) the component A and 218.7kg of MR-200 were mixed at 25 ℃ and foamed at 25 ℃ to prepare a polyurethane foam B.
Example 3
A preparation method of high-functionality polyester polyol comprises the following steps:
(1) weighing 900kg of phthalic anhydride, 350kg of terephthalic acid, 350kg of adipic acid, 800kg of glycerol, 1400kg of diethylene glycol, 500kg of ricinoleic acid, 2kg of dibutyltin dilaurate, 1kg of tetrabutyl titanate and 90kg of trimethylolpropane, and uniformly mixing;
(2) the uniformly mixed raw materials are placed in a reactor, nitrogen is introduced, the mixture is stirred, the mixture reacts for 2 hours at the temperature of 165 ℃, then the mixture is heated to 220 ℃, the mixture reacts for 4 hours at the temperature, then the mixture is heated to 230 ℃, and the mixture reacts for 6 hours at the temperature.
(3) And (3) reducing the temperature in the reactor to 200-210 ℃, and vacuumizing for 2.5h under the pressure of-0.1 MPa to obtain the high-functionality polyester polyol C.
A preparation method of high-strength polyurethane foam comprises the following steps:
(1) taking 100kg of polyester polyol C, and then uniformly mixing with 2.5kg of silicone oil, 0.7kg of deionized water, 0.3kg of PC-5, 0.8kg of PC-8, 1.5kg of K-15, 25kg of HCFC-141b and 15kg of TCPP at the temperature of 25 ℃ to obtain a component A;
(2) the component A and 218.7kg of PM-200 are mixed at 25 ℃ and foamed at 25 ℃ to prepare polyurethane foam C.
Example 4
A preparation method of high-functionality polyester polyol comprises the following steps:
(1) weighing 930kg of phthalic anhydride, 300kg of terephthalic acid, 300kg of adipic acid, 900kg of glycerol, 1300kg of diethylene glycol, 400kg of ricinoleic acid, 2kg of dibutyltin dilaurate, 1kg of tetrabutyl titanate and 90kg of trimethylolpropane, and uniformly mixing;
(2) the uniformly mixed raw materials are placed in a reactor, nitrogen is introduced, the mixture is stirred, the mixture reacts for 2 hours at the temperature of 165 ℃, then the mixture is heated to 220 ℃, the mixture reacts for 4 hours at the temperature, then the mixture is heated to 230 ℃, and the mixture reacts for 6 hours at the temperature.
(3) And (3) reducing the temperature in the reactor to 200-210 ℃, and vacuumizing for 2.5h under the pressure of-0.1 MPa to obtain the high-functionality polyester polyol D.
A preparation method of high-strength polyurethane foam comprises the following steps:
(1) taking 100kg of polyester polyol D, and then uniformly mixing with 2.5kg of silicone oil, 0.7kg of deionized water, 0.3kg of PC-5, 0.8kg of PC-8, 1.5kg of K-15, 25kg of HCFC-141b and 15kg of TCPP at 25 ℃ to obtain a component A;
(2) the component A was mixed with 218.7kg of 40V20 at 25 ℃ and foamed at 25 ℃ to prepare a polyurethane foam D.
Comparative example 1
A preparation method of polyester polyol comprises the following steps:
(1) weighing 920kg of phthalic anhydride, 300kg of terephthalic acid, 300kg of adipic acid, 400kg of glycerol, 1800kg of diethylene glycol, 600kg of ricinoleic acid, 2kg of dibutyltin dilaurate, 1kg of tetrabutyl titanate and 40kg of trimethylolpropane, and uniformly mixing;
(2) the uniformly mixed raw materials are placed in a reactor, nitrogen is introduced, the mixture is stirred, the mixture reacts for 2 hours at the temperature of 165 ℃, then the mixture is heated to 220 ℃, the mixture reacts for 4 hours at the temperature, then the mixture is heated to 230 ℃, and the mixture reacts for 6 hours at the temperature.
(3) And (3) reducing the temperature in the reactor to 200-210 ℃, and vacuumizing for 2.5h under the pressure of-0.1 MPa to obtain the high-functionality polyester polyol E.
A preparation method of polyurethane foam comprises the following specific steps:
(1) taking 100kg of polyester polyol E, and then uniformly mixing with 2.5kg of silicone oil, 0.7kg of deionized water, 0.3kg of PC-5, 0.8kg of PC-8, 1.5kg of K-15, 25kg of HCFC-141b and 15kg of TCPP at the temperature of 25 ℃ to obtain a component A;
(2) the component A was mixed with 218.7kg of MR-200 at 25 ℃ and foamed at 25 ℃ to prepare a polyurethane foam E.
Comparative example 2
A preparation method of polyester polyol comprises the following steps:
(1) weighing 920kg of phthalic anhydride, 300kg of terephthalic acid, 300kg of adipic acid, 600kg of glycerol, 1600kg of diethylene glycol, 600kg of ricinoleic acid, 2kg of dibutyltin dilaurate, 1kg of tetrabutyl titanate and 60kg of trimethylolpropane, and uniformly mixing;
(2) the uniformly mixed raw materials are placed in a reactor, nitrogen is introduced, the mixture is stirred, the mixture reacts for 2 hours at the temperature of 165 ℃, then the mixture is heated to 220 ℃, the mixture reacts for 4 hours at the temperature, then the mixture is heated to 230 ℃, and the mixture reacts for 6 hours at the temperature.
(3) And (3) reducing the temperature in the reactor to 200-210 ℃, and vacuumizing for 2.5h under the pressure of-0.1 MPa to obtain the high-functionality polyester polyol F.
A preparation method of polyurethane foam comprises the following specific steps:
(1) taking 100kg of polyester polyol E, and then uniformly mixing with 2.5kg of silicone oil, 0.7kg of deionized water, 0.3kg of PC-5, 0.8kg of PC-8, 1.5kg of K-15, 25kg of HCFC-141b and 15kg of TCPP at the temperature of 25 ℃ to obtain a component A;
(2) the component A was mixed with 218.7kg of MR-200 at 25 ℃ and foamed at 25 ℃ to prepare a polyurethane foam F.
TABLE 1 composition of the raw materials for polyester polyols A-F
The polyester polyols A to F prepared in the above examples 1 to 4 and comparative examples 1 to 2 were tested for hydroxyl value, viscosity, acid value and functionality at 25 ℃, and the test method was the conventional test method, and the test results are shown in Table 2.
TABLE 2 measurement results of physical Properties of polyester polyols A to F
| Polyester polyols | A | B | C | D | E | F |
| Hydroxyl value (mgKOH/g) | 405 | 400 | 398 | 409 | 400 | 410 |
| Viscosity (mPa)·s) | 5000 | 5500 | 4800 | 5200 | 4000 | 4500 |
| Acid value (mgKOH/mg) | 3.5 | 3.4 | 3.4 | 3.6 | 3.5 | 3.8 |
| Functionality degree | 2.7 | 2.8 | 2.7 | 2.8 | 2.2 | 2.4 |
The resulting foams were subjected to physical and chemical property tests, in which the cream time test, the fiber time test, the tack-free time test were carried out under respective foaming conditions, the density was measured according to GB/T6343-1995, and the compressive strength was measured according to GB8813-2008, with the results shown in Table 3.
TABLE 3 measurement results of physical and chemical properties of polyurethane foams
| Polyester polyols | A | B | C | D | E | F |
| Milk white time(s) | 12 | 12 | 12 | 12 | 13 | 13 |
| Fibre time(s) | 29 | 26 | 27 | 29 | 32 | 35 |
| Non-stick time(s) | 38 | 37 | 36 | 39 | 42 | 43 |
| Density (kg/m)3) | 46.1 | 46.0 | 45.5 | 46.3 | 45.6 | 46.2 |
| Compressive Strength (KPa) | 231 | 248 | 230 | 250 | 182 | 207 |
As can be seen from Table 3, the polyester polyol prepared by the formulation of the present invention produced a polyurethane foam having higher compressive strength.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art, in light of the present disclosure, will recognize that many changes may be made in the embodiments without departing from the scope and spirit of the present application.
Claims (10)
1. A high-strength polyurethane foam composition comprises a component A and a component B, and is characterized in that the component A comprises the following components in parts by weight:
the component B is isocyanate; the mass ratio of the component A to the component B is 1: 1.5-2;
the polyester polyol is prepared from the following raw materials in parts by weight:
2. the high strength polyurethane foam composition according to claim 1, wherein the second catalyst comprises dibutyltin dilaurate and tetrabutyl titanate, and the mass ratio of dibutyltin dilaurate to tetrabutyl titanate is from 1 to 2: 1.
3. The high strength polyurethane foam composition of claim 1, wherein the first catalyst comprises one or more of PC-5, PC-8, or potassium isooctanoate.
4. The high strength polyurethane foam composition of claim 1, wherein the flame retardant comprises tris- (2-chloropropyl) phosphate.
5. The high strength polyurethane foam composition of claim 1, wherein said blowing agent comprises a physical blowing agent comprising HCFC-141b and a chemical blowing agent comprising water.
6. The high strength polyurethane foam composition of claim 1, wherein the isocyanate comprises one of PM200, 44V20, or M20S.
7. A method for producing a high-strength polyurethane foam, which comprises the steps of:
(1) mixing phthalic anhydride, terephthalic acid, adipic acid, glycerol, diethylene glycol, unsaturated fatty acid, a second catalyst and trimethylolpropane according to a ratio, placing the mixture in an inert gas atmosphere, carrying out heating reaction in stages, and after the reaction is finished, vacuumizing to prepare the polyester polyol;
(2) uniformly mixing polyester polyol, silicone oil, a first catalyst, a foaming agent and a flame retardant in proportion to obtain a component A;
(3) and uniformly mixing the component A and the component B in proportion, and foaming to obtain the high-strength polyurethane foam.
8. The method of claim 7, wherein the staged heating reaction in step (1) specifically comprises: reacting for 1.5-3 h at the temperature of 150-160 ℃; reacting for 3-5 h at the temperature of 180-200 ℃; reacting for 5-8 h at the temperature of 200-230 ℃;
and/or the inert gas atmosphere is nitrogen atmosphere; and the vacuumizing time is 2-3 h.
9. The method for preparing a high-strength polyurethane foam according to claim 7, wherein the mixing temperature in the steps (2) and (3) is 10 to 35 ℃;
the foaming temperature in the step (3) is 10-35 ℃.
10. A high strength polyurethane foam prepared using the composition of any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910709898.2A CN110643011B (en) | 2019-08-02 | 2019-08-02 | High-strength polyurethane foam composition, polyurethane foam and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910709898.2A CN110643011B (en) | 2019-08-02 | 2019-08-02 | High-strength polyurethane foam composition, polyurethane foam and synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110643011A CN110643011A (en) | 2020-01-03 |
| CN110643011B true CN110643011B (en) | 2022-02-08 |
Family
ID=68990015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910709898.2A Active CN110643011B (en) | 2019-08-02 | 2019-08-02 | High-strength polyurethane foam composition, polyurethane foam and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110643011B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1487001A (en) * | 2003-08-07 | 2004-04-07 | 烟台万华聚氨酯股份有限公司 | Production process and use of polyester polyol and its modifying material |
| JP2006045435A (en) * | 2004-08-06 | 2006-02-16 | Kao Corp | Manufacturing method of rigid polyurethane foam |
| CN101851328A (en) * | 2010-06-12 | 2010-10-06 | 常州市康宏装饰材料有限公司 | High-functionality polyester polyol and preparation method thereof |
| JP2011099068A (en) * | 2009-11-09 | 2011-05-19 | Kawasaki Kasei Chem Ltd | Composition for rigid polyurethane foam and manufacturing method of rigid polyurethane foam |
| CN104262596A (en) * | 2014-09-23 | 2015-01-07 | 四川东材科技集团股份有限公司 | High-functionality degree polyester polyol and preparation method thereof |
| CN105237728A (en) * | 2015-09-23 | 2016-01-13 | 四川东材科技集团股份有限公司 | Material used for preparing rigid foamed plastic, and preparation method of rigid foamed plastic |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10472454B2 (en) * | 2012-01-18 | 2019-11-12 | Basf Se | Preparing rigid polyurethane foams |
| CN108164737B (en) * | 2017-12-27 | 2020-04-28 | 上海东大聚氨酯有限公司 | Combined polyether, polyurethane raw material composition, polyurethane foam and preparation method thereof |
| CN109749613A (en) * | 2018-12-20 | 2019-05-14 | 上海东大聚氨酯有限公司 | A kind of environmentally friendly spraying combined polyether, polyurethane foam and its feedstock composition and preparation method |
-
2019
- 2019-08-02 CN CN201910709898.2A patent/CN110643011B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1487001A (en) * | 2003-08-07 | 2004-04-07 | 烟台万华聚氨酯股份有限公司 | Production process and use of polyester polyol and its modifying material |
| JP2006045435A (en) * | 2004-08-06 | 2006-02-16 | Kao Corp | Manufacturing method of rigid polyurethane foam |
| JP2011099068A (en) * | 2009-11-09 | 2011-05-19 | Kawasaki Kasei Chem Ltd | Composition for rigid polyurethane foam and manufacturing method of rigid polyurethane foam |
| CN101851328A (en) * | 2010-06-12 | 2010-10-06 | 常州市康宏装饰材料有限公司 | High-functionality polyester polyol and preparation method thereof |
| CN104262596A (en) * | 2014-09-23 | 2015-01-07 | 四川东材科技集团股份有限公司 | High-functionality degree polyester polyol and preparation method thereof |
| CN105237728A (en) * | 2015-09-23 | 2016-01-13 | 四川东材科技集团股份有限公司 | Material used for preparing rigid foamed plastic, and preparation method of rigid foamed plastic |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110643011A (en) | 2020-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111560108B (en) | Full-water polyurethane rigid foam and preparation method and application thereof | |
| BRPI0912463B1 (en) | Process for preparing a rigid foam | |
| KR20190076963A (en) | Bio-renewable high performance polyester polyol | |
| EP0572682B1 (en) | Process for producing high-molecular aliphatic polyester, and film | |
| RU2643818C2 (en) | Method of obtaining imide-group-containing foam plastics | |
| CN110563935B (en) | High-functionality polyester polyol and preparation method thereof | |
| CN106833487A (en) | A kind of high initial bonding strength polyurethane composite gel and preparation method thereof | |
| CN112204089B (en) | Low viscosity (meth) acrylates in reactive compositions for the production of rigid polyurethane/polyisocyanurate containing foams | |
| CN110643011B (en) | High-strength polyurethane foam composition, polyurethane foam and synthesis method thereof | |
| EP3426708B1 (en) | Polyurethane and polyisocyanurate foams and methods of producing the same | |
| CN114736364B (en) | Reactive flame-retardant polyether polyol, polyisocyanurate foam, and preparation methods and applications thereof | |
| CN113621128A (en) | Safety phenolic resin modified polyurethane functional material and preparation method thereof | |
| KR20110100382A (en) | Manufacturing method of polyesterpolyol increased functionality using polyethylene terephtalate chip | |
| CN112920334B (en) | Low-shrinkage unsaturated polyester resin and preparation method thereof | |
| CN115651148B (en) | Low-density all-water foaming polyurethane rigid foam | |
| KR102548562B1 (en) | Insulating materials for refrigeration system including rigid polyurethane foams made using polyol initiated by meta-toluenediamine | |
| RU2780087C2 (en) | Polyisocyanurate-containing foam materials with long-term transition between mixing of components and transition to creamy mass and capability of instant curing | |
| JP2004352891A (en) | Method for producing polyester polyol | |
| EP3269748A1 (en) | Process for producing rigid polymer foam | |
| CN116987474A (en) | Bio-based aging-resistant polyurethane adhesive | |
| EP0333454B1 (en) | Manufacture of block polyester polyols and polyurethanes derived therefrom | |
| CA2346806A1 (en) | Polyethylene naphthalate polyester polyol and rigid polyurethane foams obtained therefrom | |
| CN117417508A (en) | Polyurethane resin and preparation method and application thereof | |
| KR20230042812A (en) | Modified recycled polyols based on the depolymerized glycolized rigid polyurethane foam scraps using glycols and a method of manufacturing the same | |
| CN115651148A (en) | Low-density full-water-blown polyurethane rigid foam |
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 |