CN109593176B - Polyurethane foam prepared by using acid-terminated oligomer as foaming agent and preparation method thereof - Google Patents
Polyurethane foam prepared by using acid-terminated oligomer as foaming agent and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- 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
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- 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
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- 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
- C08J9/141—Hydrocarbons
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- 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
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- 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
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- 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
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Abstract
The invention discloses a polyurethane foam prepared by using acid-terminated oligomer as a foaming agent and a preparation method thereof, wherein the preparation method comprises the following steps: use of a polymer terminated by an acid terminated oligomer and simultaneously satisfying (i) an acid functionality of not less than 2.0, (ii) an average molecular weight of between 300 and 900 and (iii) an acid number of between 125 and 374mgKOH/g as a blowing agent for the preparation of polyurethane foams; compared with the method that pentane is used as a foaming agent, the pentane is used as the foaming agent, so that the using amount of pentane can be reduced, and the flame retardance of the foam is improved; on the other hand, on the premise of keeping the same flame retardance, the numerical value of NCO isocyanic acid radical/OH hydroxyl mole ratio multiplied by 100 in raw materials for preparing the polyurethane foam is reduced, and the processing fluidity and the technological performance of the polyurethane foam are improved.
Description
Technical Field
The invention belongs to the technical field of polyurethane foam preparation, and particularly relates to polyurethane foam prepared by using acid-terminated oligomer as a foaming agent and a preparation method thereof.
Background
Polyurethane foam is prepared by reacting isocyanate/polyisocyanate with polyol (including polyether polyol, polyester polyol, etc.) to produce macromolecular polyurethane polymer, and simultaneously under the action of foaming agent. Among them, the blowing agent is classified into a physical blowing agent, which is a solvent having a low boiling point and is gasified to form cells under the exothermic action of the polyurethane reaction, and a chemical blowing agent, which is a substance (e.g., water, etc.) capable of participating in the polyurethane reaction and releasing gas to prepare foam.
At present, most of foaming agents such as chlorofluoroalkane, HFC fluoroalkane, chlorofluoroalkene, pentane, water and the like are adopted in the preparation process of polyurethane foam, but all the foaming agents have the following defects: chlorofluoroalkane is used as a foaming agent (such as HCFC-141b and monofluorodichloroethane), and has high ODP (ozone layer depletion potential) and GWP (greenhouse effect potential) and great environmental damage; HFC fluoroalkanes are used as foaming agents (such as HFC245fa and pentafluoropropane), have high GWP and are destructive to the environment; chlorofluoro-olefins are used as foaming agents (such as LBA and monofluorotrichloropropene), have still trace ODP and small GWP, are harmful to the environment, and are expensive and cannot be industrially produced and applied in large quantities; pentane is used as a foaming agent, so that the foaming agent is low in flash point, inflammable and explosive, has a problem in safety in use, and meanwhile, the pentane is remained in polyurethane foam, so that the flame retardant property of the polyurethane foam is very easy to be poor, and the requirements of the existing polyurethane in the fields of buildings, cold chains and the like on high flame retardant property cannot be met; water is used as a foaming agent, and reacts with polyurethane to form urea bonds, so that the polyurethane foam becomes brittle and the physical and mechanical properties become poor, and the water accelerates the polyurethane reaction, so that the process performance during the preparation of the polyurethane foam becomes poor, and the dimensional stability of the polyurethane foam prepared by using the water as the foaming agent is also poor.
At present, environmental protection, economic efficiency and other factors are considered, pentane is most commonly used as a foaming agent, but the pentane has great influence on the flame retardant property of polyurethane foam. Therefore, there is a need in the art of polyurethane foam production for a blowing agent that is environmentally friendly and economical and that improves the flame retardancy of polyurethane foams.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the application of the acid-terminated oligomer as a foaming agent for preparing polyurethane foam, and compared with the method of only adopting pentane as the foaming agent, the addition of the acid-terminated oligomer as the foaming agent can reduce the using amount of pentane so as to improve the flame retardance of the foam; on the other hand, the NCO isocyanate/OH hydroxyl molar ratio in the raw materials for preparing the polyurethane foam is reduced by 100 on the premise of keeping the same flame retardance, so that the processing flowability and the processing performance of the polyurethane foam are improved.
It is also an object of the present invention to provide polyurethane foams prepared from acid-terminated oligomers as blowing agents, having good flame retardancy, processing flow and processing properties.
The invention also aims to provide a preparation method of the polyurethane foam, which has simple process and easy operation.
The invention also aims to provide application of the polyurethane foam in preparation of building house heat-insulating layers, refrigeration house heat-insulating layers, refrigerator heat-insulating layers, container heat-insulating layers and pipeline heat-insulating layers.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the use of an acid-terminated oligomer as a blowing agent for the preparation of polyurethane foams, wherein said acid-terminated oligomer comprises a polymer terminated by an acid and simultaneously satisfies
(i) acid functionality not less than 2.0, and
(ii) an average molecular weight of 300 to 900, and
(iii) a polymer having an acid value of 125 to 374 mgKOH/g.
Preferably, the acid-terminated oligomer comprises an oligomer or fatty acid obtained by condensation of a dibasic acid and a polyol.
More preferably, the dibasic acid comprises one or a combination of more than two of suberic acid, pimelic acid, adipic acid, glutaric acid, succinic acid, terephthalic acid or phthalic anhydride; the polyalcohol comprises one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol or hexanediol.
More preferably, the fatty acids include trimer acids and/or dimer acids; wherein the chemical name of the trimer acid is octadecadienoic acid trimer, and the molecular formula is C54H56O6Is an acid-terminated oligomer having a functionality of 3; the dimer acid is named as octadecadienoic acid dimer and has a molecular formula of C36H68O4Is an acid-terminated oligomer with a functionality of 2.
In a second aspect, the polyurethane foam prepared by using the acid-terminated oligomer as a blowing agent comprises the following raw materials in parts by mass:
100-500 parts of isocyanate and/or polyisocyanate,
70-95 parts of a polyhydric alcohol,
5-30 parts of the acid-terminated oligomer,
0.1 to 30 parts of a second foaming agent,
0.1 to 10 parts of a catalyst,
0.1-5 parts of a foam stabilizer; and the raw materials meet the following requirements: when the sum of the mass percentages of the acid-terminated oligomer and the polyol is 100%, the mass percentage of the acid-terminated oligomer is 5% to 30%, and the mass percentage of the polyol is 70% to 95%.
Preferably, the said starting materials satisfy the NCO isocyanate/OH hydroxyl molar ratio X100 of a value not lower than 230.
Preferably, the polyurethane foam is a rigid polyurethane foam.
Preferably, the density of the rigid polyurethane foam is 20-200kg/m3。
In a third aspect, the method for preparing polyurethane foam by using acid-terminated oligomer as a foaming agent is characterized in that the polyurethane foam comprises the following raw materials in parts by mass:
100-500 parts of isocyanate and/or polyisocyanate,
70-95 parts of a polyhydric alcohol,
5-30 parts of the acid-terminated oligomer,
0.1 to 30 parts of a second foaming agent,
0.1 to 10 parts of a catalyst,
0.1-5 parts of a foam stabilizer; and the raw materials meet the following requirements: when the sum of the mass percentages of the acid-terminated oligomer and the polyol is 100%, the mass percentage of the acid-terminated oligomer is 5% to 30%, the mass percentage of the polyol is 70% to 95%, and the value satisfying the NCO isocyanate/OH hydroxyl molar ratio X100 is not less than 230.
In a fourth aspect, the polyurethane foam is used for preparing building house heat-insulating layers, refrigeration house heat-insulating layers, refrigerator heat-insulating layers, container heat-insulating layers and pipeline heat-insulating layers.
The invention has the beneficial effects that:
the polyurethane foam prepared by using the acid-terminated oligomer with the acid functionality not lower than 2.0 as the foaming agent has better physical and mechanical properties than the polyurethane foam prepared by using the unit acid as the foaming agent; when the molecular weight is less than 300, the acidity is high, so that the storage stability of the polyol or the polyol composition in the polyurethane raw material component is not good, and the problem can be solved by adopting the oligomer with the molecular weight of 300-900 and terminated by acid. In addition, the acid-terminated oligomers are less flammable than conventional HCFC, HFC and LBA blowing agents, do not damage the environment, are low cost and are economical.
Secondly, in the preparation process of the polyurethane foam, when the content of the acid-terminated oligomer is too high, the foaming density is too low, the reaction speed is greatly reduced, and the polyurethane foam with good mechanical property cannot be obtained; if the content is too low, the foaming effect is low, and the technical performance requirements cannot be met. The raw material of the polyurethane foam meets the requirements that when the sum of the mass percentages of the acid-terminated oligomer and the polyol is 100%, the mass percentage of the acid-terminated oligomer is 5-30%, and the mass percentage of the polyol is 70-95%, so that the polyurethane foam with good flame retardance, processing flowability and processing performance is obtained.
Thirdly, in the prior art, one of effective methods for improving the flame retardant property of the polyurethane foam is to improve the numerical value of NCO isocyanate/OH hydroxyl molar ratio multiplied by 100 of the raw materials, but after the numerical value is improved, the polyurethane foam still has stronger isocyanate trimerization reaction after foaming reaction, and the reaction temperature is higher than the foaming reaction temperature, because of the time difference between the foaming reaction and the trimerization reaction, the foaming rising rate of the system in the foaming process is reduced after being improved for a period of time, then the foaming rate is suddenly accelerated, and an obvious secondary rising peak appears, so that the problems of poor dimensional stability and cohesiveness of the polyurethane foam are caused. Compared with the method of simply adopting pentane as a foaming agent, the method has the advantages that by adding the oligomer terminated by acid as the foaming agent, on one hand, the consumption of pentane can be reduced, so that the flame retardance of the foam is improved, on the other hand, the numerical value of the NCO isocyanate/OH hydroxyl molar ratio multiplied by 100 in the raw materials can be reduced on the premise of keeping the same flame retardance, and further, the flowability and the technological performance of a polyurethane formula are improved.
Detailed Description
The technical means of the present invention will be described in detail below, but the scope of the present invention is not limited to the following examples.
The starting materials required in the following specific examples are illustrated below:
phthalic anhydride polyester polyol HF8031, Fn 2.0, hydroxyl 315, available from zhejiang huafeng new materials gmbh.
Phthalic anhydride polyester polyol HF8025, Fn 2.0, hydroxyl 240, was purchased from zhejiang huafeng new materials gmbh.
Polyether NJ4502 (sucrose + glycerol starter) Fn is 4.5 and hydroxyl is 450, available from new materials of sentencing, inc.
The acid-terminated oligomer I is prepared by a conventional condensation reaction process, is prepared by condensing 3 mol of glutaric acid and 2 mol of diethylene glycol, and has an average molecular weight of 536 and an acid value of 209 mgKOH/g.
Trimer acid, average molecular weight 841, acid functionality 3, acid number 200mgKOH/g, available from Shanghai Haorui industries, Inc.
Isocaprylic acid, molecular weight 144, acid number 390mgKOH/g, available from Chemicals, Inc., national drug group.
TCPP, tris (2-chloropropyl) phosphate, a flame retardant, purchased from Yake chemical Co., Ltd, Jiangsu.
TEP, triethyl phosphate, a flame retardant, purchased from Yarui chemical Co., Ltd, Zhang hong Kong.
L6900, silicone foam stabilizer, available from mezzanine corporation.
PC5, PC8, PC46, TMR-2 and amine catalyst, which are purchased from winning companies.
CP, cyclopentane, physical blowing agent.
Desmodur 44v20, pMDI (polymeric MDI), available from Corsaikogaku corporation.
Example 1
The preparation method of the polyurethane rigid foam high-flame-retardant discontinuous board comprises the following specific steps: fully stirring all components except isocyanate in a stirring device, namely a component A, wherein the isocyanate component is a component B, controlling the temperature of the component A and the component B at 20 ℃, quickly mixing the components together, and stirring for 5-10 seconds by using a stirrer at the speed of 2000RPM to prepare the polyurethane rigid foam; wherein, when the polyol and trimer acid are 100 parts, the trimer acid is 24.6 parts, the polyol is 75.4 parts, and the NCO isocyanate/OH hydroxyl molar ratio is 230 times 100.
Example 2
The preparation of the polyurethane rigid foam high flame-retardant non-continuous board is basically the same as the raw materials and the process of the example 1, except that 30 parts of trimer acid and 70 parts of polyol are used when 100 parts of polyol and trimer acid are used.
Example 3
A polyurethane rigid foam high flame-retardant non-continuous sheet was prepared, substantially the same as the raw materials and process of example 1, except that when the polyol and trimer acid were 100 parts, the trimer acid was 24.6 parts, the polyol was 75.4 parts, and the raw materials were adjusted so that the NCO/OH hydroxyl group molar ratio x 100 was reduced to 180.
Example 4
The polyurethane rigid foam high flame retardant non-continuous panel was prepared substantially the same as the raw materials and process of example 1, except that the polyurethane foam was prepared using the acid-terminated oligomer i.
Comparative example 1
Polyurethane foams were prepared, essentially identical to the starting materials and process of example 1, except that no trimer acid was added and pentane was used as the blowing agent.
Comparative example 2
A polyurethane foam was prepared, essentially identical to the raw materials and process of example 1, except that 35 parts of trimer acid and 65 parts of polyol were used when 100 parts of polyol and trimer acid were used.
Comparative example 3
Polyurethane foams were prepared, essentially identical to the starting materials and process of example 1, except that the trimer acid was replaced with the isocaprylic acid monobasic to prepare the polyurethane foams.
The polyurethane foams prepared in examples 1 to 4 and comparative examples 1 to 3 were subjected to the performance test, and the test methods and the relevant standards were as follows:
and (3) testing the density: GB/T6343-1995 determination of the apparent density of foams and rubbers.
Drawing time: timing is started when A, B components are mixed, a wood stick is continuously inserted into the mixture, and whether a wire drawing phenomenon exists or not is observed when the mixture is drawn out, if the wire drawing phenomenon occurs, the time is recorded as the wire drawing time, and the wire drawing time is an index for representing the reaction speed of polyurethane.
Flame retardancy: oxygen index (%), GB/T2406-93, and plastic combustion performance test method and oxygen index method test standard.
Fluidity (cm/100 g): the polyurethane mixture of the component A and the component B is poured into one end of a stainless steel mould with the length, width and thickness of 200 cm, 20 cm and 2 cm respectively, and the mould is closed. After 30 minutes the polyurethane foam was removed, tested for length and calculated for length/weight of material.
Compressive strength: GB/T8813-1988 rigid foam compression test method.
Dimensional stability: foam samples (5X 5 cm) were left at room temperature for 7 days and observed for shrinkage.
Storage stability of component a: and (3) placing the component A in an oven at 50 ℃ for 2 weeks, taking out, adding the component B according to the formula, and testing the wire drawing time. And if the drawing time is more than 20 percent of the initial drawing time of the sample after 50 ℃/2 weeks, judging that the storage stability is poor.
The raw materials, process parameters and test results are shown in table 1.
TABLE 1
As can be seen from Table 1, example 1 has an improved flame retardant performance compared to comparative example 1 using 24.6% trimer acid (calculated as 100 parts polyol + trimer acid); example 2 the flame retardant properties were improved with 30% trimer acid (calculated as 100 parts polyol + trimer acid); example 3 with 24.6% trimer acid (calculated as 100 parts of polyol + trimer acid), the NCO/OH hydroxyl molar ratio x 100 was reduced to 180, still achieving the flame retardant properties of comparative example 1, while the flowability and processing properties were significantly improved; example 4 polyurethane foams prepared with acid-terminated oligomer I also have improved flame retardant properties.
Comparative example 2 with 35% trimer acid, the foam shrunk and the reactivity (as seen from the draw time) slowed significantly, with poor overall performance; comparative example 3 polyurethane foam prepared with isooctanoic acid monobasic acid was not good in compressive strength, dimensional stability and storage stability of material a and could not be used.
Example 5
A polyurethane rigid foam high-flame-retardant continuous plate is prepared, 22.9 parts of trimer acid and pentane are added together as a foaming agent (when 100 parts of polyol and trimer acid are added), and raw materials, process parameters and test results are shown in Table 2.
Example 6
A polyurethane rigid foam high flame-retardant continuous sheet was prepared by adding 22.9 parts of trimer acid together with pentane as a blowing agent (when polyol and trimer acid are 100 parts) while reducing the NCO/OH molar ratio in the raw materials x 100 to 300, and the raw materials, process parameters and test results are shown in Table 2.
Comparative example 4
A polyurethane rigid foam high flame retardant continuous panel was prepared, which was substantially the same as the raw materials and process of example 5 except that only pentane was used as the blowing agent, and the raw materials, process parameters and test results are shown in Table 2.
TABLE 2
As can be seen from Table 2, example 5 has an improved flame retardant performance with 22.9% trimer acid as compared to comparative example 4; example 6 using 22.9% trimer acid and a reduction in the NCO isocyanate/OH hydroxyl mole ratio of the starting material by 100 to 300 still achieved the flame retardancy of comparative example 3 with significant improvements in flow and processing properties.
Claims (5)
1. Use of an acid-terminated oligomer as a blowing agent for the preparation of polyurethane foams, said acid-terminated oligomer comprising a polymer terminated by an acid and simultaneously satisfying the following conditions:
acid functionality of not less than 2.0;
(ii) an average molecular weight between 300 and 900;
(iii) a polymer having an acid value of between 125 and 374 mgKOH/g;
the acid-terminated oligomer comprises an oligomer formed by condensation reaction of dibasic acid and polyhydric alcohol; wherein:
the dibasic acid comprises one or the combination of more than two of suberic acid, pimelic acid, adipic acid, glutaric acid, succinic acid, terephthalic acid or phthalic anhydride;
the polyhydric alcohol comprises one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol or hexanediol.
2. Polyurethane foams prepared from acid-terminated oligomers as blowing agents, characterized in that,
the composite material comprises the following raw materials in parts by mass: 100 portions of isocyanate, 70 to 95 portions of polyol, 5 to 30 portions of acid-terminated oligomer in claim 1, 0.1 to 30 portions of second foaming agent, 0.1 to 10 portions of catalyst and 0.1 to 5 portions of foam stabilizer, wherein the raw materials meet the following requirements:
(a) when the sum of the mass percentages of the acid-terminated oligomer and the polyol is 100%, the mass percentage of the acid-terminated oligomer is 5% -30%, and the mass percentage of the polyol is 70% -95%; and
(b) the NCO/OH molar ratio X100 is not less than 230.
3. The polyurethane foam according to claim 2, wherein the polyurethane foam is a rigid polyurethane foam.
4. The polyurethane foam as set forth in claim 3, wherein the rigid polyurethane foam has a density of 20 to 200kg/m3。
5. Use of the polyurethane foam according to any one of claims 2 to 4 for the production of building house insulation, freezer insulation, refrigerator insulation, container insulation and pipe insulation.
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Citations (6)
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|---|---|---|---|---|
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| CN107371366B (en) * | 2015-04-07 | 2020-10-23 | 科思创德国股份有限公司 | Polyol premix composition for rigid polyurethane foams |
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