CN113637136B - Mixed foaming agent combined polyether and polyurethane hard foam - Google Patents
Mixed foaming agent combined polyether and polyurethane hard foam Download PDFInfo
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- CN113637136B CN113637136B CN202110841984.6A CN202110841984A CN113637136B CN 113637136 B CN113637136 B CN 113637136B CN 202110841984 A CN202110841984 A CN 202110841984A CN 113637136 B CN113637136 B CN 113637136B
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- C08G18/40—High-molecular-weight compounds
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- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- 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
- C08G18/425—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 the polyols containing one or two ether groups
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- 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
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- 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
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- 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
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- C08G2110/00—Foam properties
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Abstract
The invention relates to a mixed foaming agent combined polyether and polyurethane hard foam, and belongs to the technical field of high polymer materials. The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 30-50 parts of polyester polyol I; 30-40 parts of polyester polyol II; 10-40 parts of polyester polyol III; 10-15 parts of a mixed foaming agent; 2.5-3.5 parts of a catalyst I; 1.5-2.0 parts of a catalyst II; 2.5-3.0 parts of foam stabilizer; 15-30 parts of a flame retardant; the total amount of the polyester polyols I, II and III is 100 parts. Zero DOP, low GWP, low cost and environmental protection; the invention also provides the polyurethane rigid foam prepared from the mixed foaming agent combined polyether, and the polyurethane rigid foam has the advantages of good dimensional stability, excellent mechanical property, low thermal conductivity, lower feeding density, high yield and better cost saving.
Description
Technical Field
The invention relates to a mixed foaming agent combined polyether and polyurethane hard foam, and belongs to the technical field of high polymer materials.
Background
The polyurethane rigid foam is a foam product prepared from polyol and isocyanate under the action of auxiliary agents such as a foaming agent, a catalyst and the like, has excellent thermal insulation performance and better mechanical property, simultaneously has excellent electrical property and chemical resistance, and is widely applied to the thermal insulation fields of refrigerators, freezers, water heaters, cold storage plates, pipeline thermal insulation, refrigerated containers, external wall thermal insulation and the like. The blowing agents currently used in the production of rigid polyurethane foams are mainly HCFC141b, cyclopentane and HFC-365mfc. Three blowing agents each have disadvantages: when HCFC141B was used, there was a certain ODP (ozone depletion potential) and the Montreal protocol implemented complete industrial phase-out for HCFC141B in 2026. When cyclopentane is adopted, the output rate is low, the safety coefficient is low, and the dimensional stability is poor; when HFC-365mfc is used for preparing the foam, although the foam has low heat conductivity coefficient and better heat insulation performance, the safety coefficient is low, the cost is higher, and the cost of the prepared foam is obviously increased. For this reason, there is a need in the art to develop a blowing agent system that is low in cost, low in thermal conductivity, zero in ODP value, relatively high in safety factor, good in dimensional stability, excellent in mechanical properties, and high in squareness.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides the mixed foaming agent combined polyether which can reach zero DOP, low GWP, low cost and environmental protection; the invention also provides the polyurethane rigid foam prepared by the mixed foaming agent combined polyether, and the polyurethane rigid foam has the advantages of good dimensional stability, excellent mechanical property, low thermal conductivity, lower feeding density, high yield and better cost saving.
In order to achieve the purpose, the invention provides the following technical scheme:
the mixed foaming agent composite polyether is characterized by comprising the following raw materials in parts by weight:
30-50 parts of polyester polyol I;
30-40 parts of polyester polyol II;
10-40 parts of polyester polyol III;
10-15 parts of a mixed foaming agent;
2.5-3.5 parts of a catalyst I;
1.5-2.0 parts of a catalyst II;
2.5-3.0 parts of foam stabilizer;
15-30 parts of a flame retardant;
the total amount of the polyester polyols I, II and III is 100 parts;
the mixed foaming agent is a mixture of water, formic acid and n-pentane, and the mass ratio of the water to the formic acid to the n-pentane is (5-10): (7-12): (80-90);
the polyester polyol I is polyester polyol with the viscosity of 2500-4000mPa & s (detected at 25 ℃) and the hydroxyl value of 225-255mgKOH/g, and polyester 2412 of Nanjing Jinling Spatan chemical company Limited is adopted; or the company Ruinor chemical Co., ltd PS2412;
the polyester polyol II is polyester polyol with the viscosity of 10000-30000mPa & s (detected at 25 ℃) and the hydroxyl value of 170-205mgKOH/g, and polyester 1919A of Nanjing Jinling Spandel chemical company Limited is adopted; or the company PS3025 of ryinow chemical ltd;
the polyester polyol III is polyester polyol with the viscosity of 2000-4000mPa & s (detected at 25 ℃) and the hydroxyl value of 280-330mgKOH/g, and polyester 3152 of Nanjing Jinling Spodopan chemical company Limited is adopted; or Reynolds chemical Co., ltd PS3152; or Nanguang polyester Co., ltd 3152;
the catalyst I is a tertiary amine catalyst;
the catalyst I adopts any two or a mixture of more than two of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, triethylenediamine, tetramethylalkylenediamine, pentamethyldiethylenetriamine, triethylamine, N, N-dimethylbenzylamine, N, N-dimethylhexadecylamine and 2-hydroxy-N, N, N-trimethyl-1-propylamine formate;
the catalyst II is an organic metal salt catalyst;
the catalyst II adopts any one or a mixture of two of potassium isooctanoate, potassium oleate and potassium acetate;
the foam stabilizer has the main functions of increasing the intersolubility of all components of the combined polyether and stabilizing the cell structure, and adopts any one of the foam stabilizers of L-16268, L-6866 and L-16368 of a new material group in a Mianji diagram; or MG687 or B84813 originated from specialty Chemicals (Shanghai) Inc.; or any one of AK8805, AK8806, AK8810, AK8811, AK8818, which are available from Meisida chemical Co., ltd;
the flame retardant is one or a mixture of two of tris (2-chloropropyl) phosphate, tris (2-chloroethyl) phosphate, tris (1, 3-dichloroisopropyl) phosphate or dimethyl methyl phosphate.
The rigid polyurethane foam is characterized by comprising a component A and a component B, wherein the component A is prepared by mixing the following components in a ratio of 1: (1.4-1.8), mixing and foaming, wherein the component A is the mixed foaming agent combined polyether, and the component B is isocyanate;
the isocyanate adopts PM200 or PM400 of Wanhua chemistry;
the mixing and foaming adopt a high-pressure foaming machine, and the foaming temperature is controlled at 20-25 ℃.
The invention has the advantages that: the mixed foaming agent composite polyether of the invention adopts the mixture of water, n-pentane and formic acid, has zero DOP, low GWP, ultra-low cost (the price is 1/6-1/4 of that of HCFC and HFC series common foaming agents), is green and environment-friendly; the foaming agent involved in the invention is prepared by reacting water with isocyanate to generate substituted urea and carbon dioxide and release a large amount of heat; the formic acid reacts with the tertiary amine catalyst to form salt in the initial stage, the salt does not participate in the reaction in the initial stage, the salt releases tertiary amine to catalyze the reaction to be carried out at a high speed along with the violent heat release of the reaction, and meanwhile, the carboxylic acid reacts with isocyanate to generate amide and carbon dioxide and releases certain heat; the heat released by the two promotes the volatilization of n-pentane, thereby promoting the foaming process of polyurethane and increasing the foaming multiplying power. The polyurethane rigid foam has the advantages of good dimensional stability, excellent mechanical property and low heat conductivity coefficient, and the polyurethane rigid foam has lower feeding density (compared with H)The CFC141b system can be lowered by 2-3kg/m 3 ) The formula ratio is high, the cost can be better saved, and the low hydroxyl value polyester is selected to ensure that the whole system has higher isocyanate index, thereby being beneficial to improving the strength of foam; the n-pentane and formic acid are used as foaming agents, the molecular weights of the n-pentane and formic acid are smaller than that of HCFC141b, HFC-365mfc and the like, and the foaming ratio is better.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight:
2412 parts of spandex polyester polyol, 30 parts of spandex polyester polyol, 3152 parts of spandex polyester polyol, 1.0 part of water, 1.3 parts of formic acid, 12 parts of N-pentane, 0.6 part of pentamethyldiethylenetriamine, 0.4 part of N, N-dimethylcyclohexylamine, 2.3 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.7 parts of potassium isooctanoate, 1.2 parts of AK8805, 5 parts of MG6871.5 parts of tris (2-chloropropyl) phosphate and 20 parts of tris (2-chloropropyl) phosphate.
The rigid polyurethane foam of this example includes component A comprising the mixed blowing agent and polyether polyol, and component B comprising 198.8 parts isocyanate.
And uniformly mixing the component A and the component B, and reacting to prepare the polyurethane rigid foam. Specifically, a one-step foaming process is adopted, the combined foaming agent obtained in the embodiment is foamed with the polyether and the isocyanate in a high-pressure foaming machine, and the temperature is controlled to be 20-25 ℃.
Example 2
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 30 parts of PS-2412, 30240 parts of Reno polyester polyol, 3152 parts of Reno polyester polyol, 0.95 part of water, 1.15 parts of formic acid, 12.5 parts of N-pentane, 0.6 part of pentamethyldiethylenetriamine, 0.4 part of N, N-dimethylcyclohexylamine, 2.2 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.8 parts of potassium isooctanoate, 1.2 parts of AK8805, 71.4 parts of M, and 20 parts of tris (2-chloroethyl) phosphate.
The rigid polyurethane foam comprises an A component consisting of the mixed foaming agent combined polyether and a B component consisting of 206.2 parts of isocyanate.
Example 3
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 24140 parts of reyno polyester polyol, 3025 parts of reyno polyester polyol, 3152 parts of reyno polyester polyol, 0.9 part of water, 1.1 parts of formic acid, 13 parts of N-pentane, 0.6 part of pentamethyl diethylene triamine, 0.4 part of N, N-dimethyl cyclohexylamine, 2.3 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.8 parts of potassium oleate, 1.0 part of AK8805, 162L 681.6 parts of tris (1, 3-dichloroisopropyl) phosphate and 20 parts of tris (1, 3-dichloroisopropyl) phosphate.
The rigid polyurethane foam of the embodiment comprises an A component consisting of the mixed foaming agent combined polyether and a B component consisting of 214 parts of isocyanate.
Example 4
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 24140 parts of Spandex polyester polyol, 1919A 40 parts of Spandex polyester polyol, 3152 parts of Nanguano polyester polyol, 0.95 part of water, 1.5 parts of formic acid, 11 parts of N-pentane, 0.65 part of bis (2-dimethylaminoethyl) ether, 0.5 part of N, N-dimethylcyclohexylamine, 2.3 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.75 parts of potassium isooctanoate, 2.8 parts of L16368 and 20 parts of tris (1, 3-dichloroisopropyl) phosphate.
The rigid polyurethane foam of the embodiment comprises an A component composed of the mixed foaming agent combined polyether and a B component composed of 226 parts of isocyanate.
Example 5
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 2412 parts of Spirascid polyester polyol, 3025 parts of Renao polyester polyol, 3152 parts of Renao polyester polyol, 1.0 part of water, 1.35 parts of formic acid, 12 parts of N-pentane, 0.6 part of bis (2-dimethylaminoethyl) ether, 0.6 part of N, N-dimethylcyclohexylamine, 2.3 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.8 parts of potassium oleate, 2.8 parts of MG687, and 20 parts of tris (1, 3-dichloroisopropyl) phosphate.
The rigid polyurethane foam comprises an A component consisting of the mixed foaming agent combined polyether and a B component consisting of 241.8 parts of isocyanate.
Example 6
The mixed foaming agent composite polyether comprises the following raw materials in parts by weight: 2412 parts of reyno polyester polyol, 3025 parts of reyno polyester polyol, 3152 parts of southern gloss polyester polyol, 0.95 part of water, 1.45 parts of formic acid, 11 parts of N-pentane, 0.65 part of bis (2-dimethylaminoethyl) ether, 0.55 part of N, N-dimethylcyclohexylamine, 2.3 parts of 2-hydroxy-N, N, N-trimethyl-1-propylamine formate, 1.8 parts of potassium isooctanoate, 1.0 part of AK 8811.0 part of L-6866.8 part of dimethyl methyl phosphate, and 20 parts of dimethyl methyl phosphate.
The rigid polyurethane foam comprises a component A consisting of the mixed foaming agent combined polyether and a component B consisting of 255 parts of isocyanate.
The core density, oxygen index, thermal conductivity, compressive strength, drawing strength and high and low temperature dimensional change rate of the foam are respectively determined according to national standards GB/T6343-2009, GB/T8624-2012, GB/T10295-2008, GB/T8813-2008, GB/T23932-2009 and GB/T8811-2008. The following table compares the performance parameters of the rigid polyurethane foams obtained in examples 1 to 6 with those of the prior art:
as can be seen from the above examples and comparative tables, compared with the prior art (adopting HCFC141B/HFC245fa/HFC365 mfc/cyclopentane, etc.), the mixed foaming agent system of the invention has the advantages of lower foam preparation cost, larger foaming ratio, lower thermal conductivity, better heat preservation effect, better dimensional stability and excellent mechanical property.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The mixed foaming agent composite polyether is characterized by comprising the following raw materials in parts by weight:
30-50 parts of polyester polyol I;
30-40 parts of polyester polyol II;
10-40 parts of polyester polyol III;
10-15 parts of a mixed foaming agent;
2.5-3.5 parts of a catalyst I;
1.5-2.0 parts of a catalyst II;
2.5-3.0 parts of foam stabilizer;
15-30 parts of a flame retardant;
the total amount of the polyester polyols I, II and III is 100 parts;
the mixed foaming agent is a mixture of water, formic acid and n-pentane, and the mass ratio of the water to the formic acid to the n-pentane is (5-10): (7-12): (80-90);
the polyester polyol I is polyester polyol with the viscosity of 2500-4000mPa & s and the hydroxyl value of 225-255 mgKOH/g;
the polyester polyol II is polyester polyol with the viscosity of 10000-30000mPa & s and the hydroxyl value of 170-205 mgKOH/g;
the polyester polyol III is polyester polyol with the viscosity of 2000-4000mPa & s and the hydroxyl value of 280-330 mgKOH/g;
the polyester polyol I adopts polyester 2412 of Nanjing Jinling Span chemical Limited company; or Reno chemical Limited PS2412;
the polyester polyol II adopts polyester 1919A of Nanjing Jinling Span chemical Limited company; or Reynolds chemical Co., ltd, PS3025;
the polyester polyol III adopts polyester 3152 of Nanjing Jinling Spatan chemical Co.Ltd; or the company Reno chemical company PS3152; or Nanguang polyester Co., ltd 3152.
2. A mixed blowing agent conjugate polyether as claimed in claim 1, characterized in that the catalyst I is a tertiary amine catalyst; the catalyst II is an organic metal salt catalyst.
3. A mixed blowing agent composite polyether according to claim 2, characterized in that said catalyst I is a mixture of any two or more of N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, triethylenediamine, tetramethylalkylenediamine, pentamethyldiethylenetriamine, triethylamine, N, N-dimethylbenzylamine, N, N-dimethylhexadecylamine, 2-hydroxy-N, N, N-trimethyl-1-propylamine formate;
the catalyst II is any one or a mixture of two of potassium isooctanoate, potassium oleate and potassium acetate.
4. A mixed blowing agent conjugate polyether as claimed in claim 1, characterized in that
The foam stabilizer is any one of L-16268, L-6866 and L-16368 of Mianji advanced materials group; or MG687 or B84813 originated from specialty Chemicals (Shanghai) Inc.; or any of AK8805, AK8806, AK8810, AK8811, and AK8818, which are available from Meisida chemical Co., ltd.
5. A mixed blowing agent conjugate polyether as claimed in claim 1, characterized in that
The flame retardant is one or a mixture of tri (2-chloropropyl) phosphate, tri (2-chloroethyl) phosphate, tri (1, 3-dichloroisopropyl) phosphate or dimethyl methyl phosphate.
6. Polyurethane rigid foam produced using the mixed blowing agent-polyether composition according to any of claims 1 to 5, characterized by comprising a component A and a component B, which are mixed in a ratio of 1: (1.4-1.8), wherein the component A is the mixed foaming agent conjugate polyether as described in any one of claims 1-5, and the component B is isocyanate.
7. The rigid polyurethane foam according to claim 6, wherein the mixing and foaming are performed by a high pressure foaming machine at a foaming temperature of 20 to 25 ℃.
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