LBA system polyurethane composite A material and preparation method thereof
By combining specific catalysts and surfactants, the compatibility and chemical stability issues of LBA foaming agent in polyurethane composites have been resolved, resulting in improved long-term storage stability and foam performance. This technology is suitable for applications such as building exterior wall insulation, cold chain logistics, refrigerators and freezers, and industrial pipeline insulation.
Patent Information
- Application Number
- CN202610003781.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-05
- Publication Date
- 2026-02-17
AI Technical Summary
LBA blowing agent has poor compatibility and chemical instability issues in polyurethane blends, resulting in short shelf life and rapid performance degradation, which affects the stability of the foaming process and foam performance.
By combining tertiary amine catalysts with tetraalkylguanidine substances of specific structures, along with a blend of silicon-based and non-silicone surfactants, the nucleophilic attack ability and chemical activity of LBA are reduced. At the same time, acidic substances are neutralized by crosslinking agents, ensuring the long-term storage stability and foaming performance of the blend.
It achieves long-term storage stability of polyurethane component A in the LBA system, ensures uniform and dense foam structure, improves construction quality and efficiency, broadens the tolerance of spraying processes, and provides an environmentally friendly and easily promoted industrial formula.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of polyurethane materials technology, and in particular to an LBA system polyurethane composite A material and its preparation method. Background Technology
[0002] Rigid polyurethane foam, due to its extremely low thermal conductivity, high specific strength, and excellent molding ability, is widely used in building exterior wall insulation, cold chain logistics, refrigerators and freezers, industrial pipeline insulation, and other fields, making it one of the most efficient polymer insulation materials currently available. It is typically produced by the reaction of two components: Component A (commonly known as the white component) contains polyether / polyester polyol, catalyst, foam surfactant, blowing agent, etc.; Component B (commonly known as the black component) is mainly isocyanate.
[0003] In the preparation of rigid polyurethane foam, physical blowing agents are crucial, directly affecting the foam's thermal conductivity, density, and environmental performance. With increasingly stringent environmental regulations, physical blowing agents have evolved from ozone-depleting CFC-11 to the transitional HCFC-141b, and now to the mainstream but high-GWP HFCs (such as HFC-245fa and HFC-365mfc).
[0004] Fourth-generation hydrofluoroolefin blowing agents, represented by trans-1-chloro-3,3,3-trifluoropropylene (HFO-1233zd(E), commonly abbreviated as LBA in the industry), are widely recognized as one of the most ideal choices to replace high-GWP HFC blowing agents due to their zero ozone depletion potential (ODP), extremely low GWP (<1), non-flammability, and excellent thermal conductivity similar to HFC-245fa.
[0005] However, in practical industrial applications, the long-term storage stability of LBA when formulated into premixed component A mixtures is a technical bottleneck that urgently needs to be addressed. This problem mainly manifests as follows:
[0006] (1) Phase separation due to poor compatibility: LBA has limited compatibility with some types of polyether polyols, especially in the presence of components such as amine catalysts. During storage, LBA is prone to precipitate from the composite material, causing stratification and resulting in uneven system, which seriously affects the stability of subsequent foaming process and foam performance.
[0007] (2) Decomposition due to chemical instability: This is a more critical and fatal problem. The LBA molecule contains unsaturated double bonds and chlorine atoms, making it chemically reactive. In the alkaline environment commonly found in component A (especially the alkaline environment provided by amine catalysts), LBA is prone to elimination reactions or nucleophilic substitution reactions, such as dehydrochlorination, leading to decomposition. This decomposition triggers a series of chain-like negative effects: ① Consumption of effective foaming agent, resulting in a decrease in the actual content of foaming agent in the composite material, a decrease in the foaming ratio, and an increase in foam density; ② Production of acidic substances. The acid produced by decomposition neutralizes and poisons the amine catalyst, leading to a significant decrease in the activity of the composite material, manifested as a significant extension of the milky white time and gel time during foaming, or even the inability to foam normally or the occurrence of serious defects such as foam collapse.
[0008] To address the aforementioned issues, those skilled in the art have made several attempts, but all have significant shortcomings: some solutions attempt to improve compatibility using polyether polyols with specific structures, but these are often costly and have limited effectiveness in inhibiting the chemical decomposition of LBA. Other solutions involve adding acidic substances or surfactants to inhibit decomposition, but if the type and amount are not properly selected, they can easily conflict with other components in the system (such as catalysts) or negatively impact the physical properties of the final foam (such as dimensional stability and strength). Therefore, existing technologies lack a systematic and synergistic solution to address the dual challenges of LBA compatibility and chemical stability in compound formulations. This results in existing LBA compound formulations generally having short shelf lives (typically less than 3 months) and rapid performance degradation, severely restricting their large-scale production and commercial application.
[0009] In summary, there is an urgent need in this field to develop a new LBA system polyurethane blend and its preparation method. This method can fundamentally suppress the decomposition and phase separation of LBA without sacrificing the foaming process performance and the final foam physical properties, thereby achieving long-term (e.g., more than 6 months) storage stability of the blend to meet the requirements of industrial production and storage. Summary of the Invention
[0010] Purpose of the invention: The first purpose of the invention is to provide an improved LBA system polyurethane composition A material, which enhances storage stability and addresses the problem of foam collapse after foaming; the second purpose of the invention is to provide a method for preparing the LBA system polyurethane composition A material.
[0011] The LBA system polyurethane composition A of the present invention, by weight, comprises: 8-12 parts of polyether polyol, 40-45 parts of polyester polyol, 20-25 parts of liquid flame retardant, 5-7 parts of crosslinking agent, 2-3 parts of surfactant, 9-10 parts of catalyst, and 0.3-0.5 parts of additives; 0.8-1 parts of chemical foaming agent and 9-10 parts of physical foaming agent; the B component is polymethylene polyphenyl polyisocyanate; the catalyst includes tertiary amine catalysts and organometallic catalysts; the additives are tetraalkylguanidine substances; and the surfactants include silicone and non-silicone surfactants.
[0012] Preferably, the non-silicone surfactant is S1021.
[0013] Preferably, the silicon-based surfactant is B8545 or B8534.
[0014] Preferably, the mass ratio of the silicone surfactant to the non-silicone surfactant is 1:1~2. The simultaneous use of silicone and non-silicone surfactants achieves synergistic complementarity. Silicone surfactants provide strong dynamic foam stabilization and precise cell structure control in the LBA system, while the core role of non-silicone surfactants in the LBA system is to assist emulsification, improve compatibility, and enhance storage stability. A certain ratio of these two surfactants can effectively alleviate the turbidity phenomenon in the polyurethane A component of the LBA system due to poor storage stability, while also reducing the occurrence of coarse foam or even foam collapse caused by poor material mixing during spraying.
[0015] Preferably, the tertiary amine catalyst is Xinrui Cat208, Xinrui Cat214, or Huntsman H1. Using tertiary amines with large steric hindrance or electron-withdrawing functional groups can effectively reduce the nucleophilic attack ability of their nitrogen atoms on LBA, making them less prone to dehydrohalogenation reactions in alkaline or nucleophilic environments.
[0016] Preferably, the tetramethylguanidine is tetramethylguanidine (TMG). Tetraalkylguanidines (such as tetramethylguanidine) combine with tertiary amine catalysts that have large steric hindrance or electron-withdrawing functional groups, reducing the basicity and nucleophilicity of the amine, making it more stable during storage, and restoring its activity when it is thermally decomposed during foaming.
[0017] Preferably, the organometallic catalyst is PC46, K15, T-12, or T-120.
[0018] The mass ratio of the tertiary amine catalyst to the organometallic catalyst is 7-8:1.
[0019] Preferably, the polyether polyol is NJ-6249 or NJ-6305C.
[0020] Preferably, the polyester polyol is SKR-240B or Terol-250.
[0021] Preferably, the crosslinking agent is TEOA or NJ-403. TEOA is triethanolamine, and NJ-403 is ethylenediamine initiator polyether; both are alkaline and can neutralize acidic substances generated during the aging process of the composite material. Both also possess certain reactivity, providing some protection to the composite material.
[0022] Preferably, the liquid flame retardant is a halophosphate ester-added flame retardant, selected from at least one of tri(chloropropyl) phosphate (TCPP) and tri(dichloropropyl) phosphate (TDCPP), which are difficult to hydrolyze.
[0023] The preparation method of polyurethane composition A in the LBA system of the present invention includes the following steps:
[0024] (1) Add the raw materials of component A, excluding the foaming agent and additives, to the reactor and mix them evenly;
[0025] (2) Add tetramethylguanidine substances, cool down to below 14°C during stirring, add chemical foaming agent and physical foaming agent, stir evenly, and you can get the A component of the LBA system with excellent storage stability.
[0026] Preferably, in step (2), the mixing process conditions are as follows: indoor temperature ≤28℃, humidity 60±10%, stirring power IBC: 200-400HZ, reaction vessel: 60-80HZ, and total stirring time ≥90min.
[0027] Mechanism of Invention: Due to the presence of Cl atoms and unsaturated double bonds in the LBA molecule, it is prone to dehydrohalogenation under alkaline or nucleophilic conditions (especially in the presence of commonly used tertiary amine catalysts), leading to its decomposition. This not only consumes the foaming agent but also produces acidic substances (such as HCl). The negative impact of these acidic substances is that they neutralize the catalyst, and the generated HCl neutralizes the amine catalysts in the system, resulting in reduced activity of the composite material, prolonged milky white time and gel time during foaming, or even no reaction and foam collapse.
[0028] This invention utilizes amines with specific structures, employing tertiary amines with significant steric hindrance or electron-withdrawing functional groups to reduce the nucleophilic attack capability of their nitrogen atoms on LBA. Tetraalkylguanidines (such as tetramethylguanidine), combined with the aforementioned specific amine catalysts, reduce the basicity and nucleophilicity of the amines, making them more stable during storage and restoring activity upon thermal decomposition during foaming. Secondly, the crosslinking agent added to the composite material of this invention is a basic amine polyether, which to some extent protects the amine catalyst from neutralization by acidic substances. Finally, the composite material of this invention employs both silicone and non-silicone surfactants. Silicone surfactants provide strong dynamic foam stability and precise control of cell structure in the LBA system, while the core role of non-silicone surfactants in the LBA system is to assist emulsification, improve compatibility and storage stability, unexpectedly solving the problem of foam collapse after foaming in the LBA system composite material after long-term storage.
[0029] Beneficial effects: Compared with the prior art, the present invention has the following advantages: (1) The polyurethane composition A of the LBA system of the present invention significantly improves the long-term storage stability of the A composition in the LBA system, solves the industry problem of activity decay caused by traditional catalysts, and enables the A composition to be stably stored at room temperature for at least 6 months; (2) The present invention achieves finely controlled foam structure and excellent comprehensive performance, and innovatively combines silicone and non-silicone surfactants to play an extraordinary synergistic role. This design ensures that after long-term storage, the foam of the LBA system A composition still has a uniform and dense closed structure. The porous structure ensures low water absorption and low thermal conductivity; (3) This invention broadens the process tolerance of spraying construction and improves construction performance. Specifically, the use of composite surfactants and specific catalyst systems reduces defects such as flow and voids in the spraying process, thereby improving construction quality and efficiency; (4) This invention provides an efficient, environmentally friendly and highly operable overall solution. Through the linkage design of catalyst and surfactant systems, it successfully adapts to environmentally friendly LBA foaming agent, providing a stable and easy-to-promote industrial formulation solution to replace traditional high global warming potential (GWP) foaming agents. Detailed Implementation
[0030] The present invention will be further described below with reference to specific embodiments.
[0031] The raw materials used in the embodiments of the present invention are shown in Table 1. The pure water meets the quality specifications of Grade III water in GB / T 6682-2016.
[0032] Table 1 Raw Material List
[0033]
[0034] Example 1
[0035] The LBA system polyurethane composition A of the present invention comprises, by weight: 8 parts of polyether polyol NJ-6249, 45 parts of polyester polyol Terol-250, 20 parts of liquid flame retardant TCPP, 5 parts of crosslinking agent NJ-403, 1 part of silicone surfactant B8534, 1 part of non-silicone surfactant S1021, 8.4 parts of specific tertiary amine catalyst (2.4 parts of Cat208, 44 parts of Cat21, and 2 parts of H1), 1.2 parts of organometallic catalyst (0.6 parts of PC46, 0.3 parts of K15, and 0.3 parts of T12), 0.3 parts of additive TMG, 1 part of chemical foaming agent water, and 9 parts of physical foaming agent LBA.
[0036] The preparation method includes the following steps:
[0037] (1) Add the raw materials of polyurethane composition A in the LBA system, excluding the foaming agent and tetramethylguanidine additive, to the reactor;
[0038] (2) Start stirring and stir evenly for 10 min. Add tetramethylguanidine adjuvant. During the stirring process, cool down to 14℃ through the condensate in the jacket of the reactor and add LBA foaming agent. Continue stirring for 30 min to obtain component A of the LBA system with excellent storage stability. In step (2), the mixing process conditions are required as follows: indoor temperature ≤28℃, humidity 60±10%, stirring power IBC: 200-400HZ, reactor: 60-80 HZ, and total stirring time ≥90min.
[0039] The components and proportions (parts by weight) of the remaining embodiments and comparative examples are shown in Table 2.
[0040] Comparative Example 1
[0041] Based on Example 2, the specific tertiary amine catalyst was replaced with a conventional tertiary amine catalyst, and the remaining steps were the same.
[0042] Comparative Example 2
[0043] Based on Example 2, the adjuvant TMG was removed, and the remaining steps were the same.
[0044] Comparative Example 3
[0045] Based on Example 2, all non-silicone surfactants were replaced with silicone surfactants, while the rest remained the same.
[0046] Comparative Example 4
[0047] Based on Example 2, all silicone surfactants were replaced with non-silicone surfactants, while the rest remained the same.
[0048] Comparative Example 5
[0049] Based on Example 2, the ratio of silicone surfactant to non-silicone surfactant was changed to 2:1, and the remaining steps were the same.
[0050] Comparative Example 6
[0051] Based on Example 2, the ratio of a specific tertiary amine catalyst to a metal catalyst was changed to 1:1, while the remaining steps remained the same.
[0052] Table 2. Parts by weight of each component raw material in the Examples and Comparative Examples
[0053]
[0054] The polyurethane composite A material of the LBA system prepared in Table 2 was placed in a 50℃ oven for 2 weeks. After 2 weeks, the transparency of the composite material was observed. 100 g of the composite material was foamed with the same mass of PAPI at 20℃. The physical property test data are shown in Table 3.
[0055] Table 3 Performance test data for the examples and comparative examples
[0056]
[0057] (Note: The blank group consists of test data at room temperature before oven drying.)
[0058] After two weeks of storage stability testing, all data in Examples 1-3 were normal. This was mainly because the specific tertiary amine catalyst and tetraalkylguanidine substances improved the long-term storage stability of the A-material composition in the LBA system, while the combination of silicone surfactants and non-silicone surfactants gave the A-material composition both strong dynamic foam stabilization ability and compatibility.
[0059] Comparative Example 1 replaced the specific tertiary amine catalyst with a conventional tertiary amine catalyst based on Example 2. The activity of the combined material was accelerated by drying in a 50°C oven for 2 weeks, which greatly reduced the reactivity.
[0060] Comparative Example 2 is based on Example 2, but the additive TMG is removed. The reactivity is slightly reduced because TMG can restore the reactivity of compound A to a certain extent during the foaming process. Removing TMG slightly reduces the reactivity.
[0061] Comparative Example 3 used only silicone surfactants, resulting in poor emulsification performance and compatibility issues with the combined materials. This led to foam collapse during the foaming process, resulting in poor foam formation, low closed-cell rate, and high thermal conductivity.
[0062] Comparative Example 4 used only non-silicone surfactants, which had poor foam stabilization and nucleation capabilities, and exhibited slight foam collapse during the foaming process. The large pores resulted in low closed-cell rate and high thermal conductivity.
[0063] Comparative Example 5: When the ratio of silicone surfactant to non-silicone surfactant was changed, a higher proportion of silicone surfactant resulted in bubble collapse and unsatisfactory performance.
[0064] Comparative Example 6 reduced the proportion of a specific tertiary amine catalyst compared to Example 2. With the total amount of catalyst remaining unchanged, the content of foaming catalyst decreased, the content of metal catalyst increased, the milky whitening time was significantly prolonged, and the reaction activity of the combined material still showed a decline.
Claims
1. An LBA system polyurethane composition A-material, characterized in that, By weight parts include: polyether polyol 8~12 parts, polyester polyol 40~45 parts, liquid flame retardant 20~25 parts, crosslinking agent 5~7 parts, surfactant 2~3 parts, catalyst 9~10 parts, auxiliary 0.3~0.5 parts; chemical blowing agent 0.8~1 parts, physical blowing agent 9~10 parts;The catalyst includes tertiary amine catalyst with larger steric hindrance or electron withdrawing functional groups and organic metal catalyst;The auxiliary is a tetraalkyl guanidine substance;The surfactant includes silicon and non-silicone surfactant.
2. The LBA system polyurethane composition A material according to claim 1, characterized by, The non-silicone surfactant is S1021.
3. The LBA system polyurethane composition A material according to claim 1, characterized by, The silicon surfactant is B8545 or B8534.
4. The LBA system polyurethane composition A material according to claim 1, characterized by, The mass ratio of the silicon surfactant to the non-silicone surfactant is 1:1~2.
5. The LBA system polyurethane composition A material according to claim 1, characterized in that, The tetramethyl guanidine substance is tetramethyl guanidine.
6. The LBA system polyurethane composition A material according to claim 1, characterized by, The tertiary amine catalyst is Xinxue Cat208, Xinxue Cat214, Huntsman H1.
7. The LBA system polyurethane composition A material according to claim 1, characterized by, The organic metal catalyst is PC46, K15, T-12, T-120.
8. The LBA system polyurethane composition A material according to claim 1, characterized by, The mass ratio of the tertiary amine catalyst to the organic metal catalyst is 7~8:
1.
9. The LBA system polyurethane composition A material according to claim 1, characterized in that, The crosslinking agent is TEOA, NJ-403.
10. A process for the preparation of the LBA-system polyurethane composition A according to any one of claims 1 to 9, characterized in that It includes the following steps: (1) Put the raw materials except the blowing agent and the auxiliary in the LBA system polyurethane combination A material into the reaction kettle and mix uniformly; (2) Add tetramethyl guanidine substance, cool to below 14℃ during stirring, add chemical blowing agent and physical blowing agent, and stir uniformly to obtain excellent storage stable LBA system A component.