A polyether-modified silicone oil and a method for producing the same, a polyurethane foam composition

Abstract

The application discloses a polyether modified silicone oil with improved polyol compatibility and application of the polyether modified silicone oil in a polyurethane foam composition. The polyether modified silicone oil has a structure comprising the following segments: (a) a polyoxyethylene ether segment; and (b) an alkylated polyoxyethylene polyoxypropylene ether segment, wherein EO and PO can be randomly copolymerized or block copolymerized. The mass ratio of the polyoxyethylene ether segment to the alkylated polyoxyethylene polyoxypropylene ether segment is 1:0.6-4, preferably 1:1-2. The polyurethane composition comprises an A component and a B component. The A component is an isocyanate-reactive component, and comprises a polyol, a catalyst, a blowing agent and the polyether modified silicone oil. The B component is an isocyanate component. The polyether modified silicone oil has the functions of a compatibility agent and a foam stabilizer, the polyurethane composition has good storage and foaming stability, and the polyurethane foam material can be prepared.

Description

Technical Field

[0001] This invention relates to the field of polyurethane foam material preparation technology, and more specifically, to a polyether-modified silicone oil with improved polyol compatibility and its preparation method, which can be applied to polyurethane foam compositions. Background Technology

[0002] Polyurethane possesses foamability, high adhesion, high elasticity, and insulation properties, making it suitable for manufacturing various products. It is the only organic polymer material with widespread applications in foams, plastics, and coatings. Polyurethane foam, as one of the most widely used polyurethane products, boasts numerous excellent properties and plays an indispensable role in daily life.

[0003] Currently, most polyurethane foams are prepared using a one-step process, which involves reacting isocyanate reactive components (such as polyols, blowing agents, catalysts, and surfactants) with isocyanates to form foam. The polyol mixture acts as the active component, reacting with the isocyanate; therefore, the performance of polyurethane foam largely depends on the composition and structure of the polyol mixture. In the industrial production of polyurethane foam, various types of polyols are used. However, different types of polyols may exhibit incompatibility due to differences in structure, molecular weight, etc. This compatibility directly affects the storage stability of the polyol mixture and can lead to instability in polyurethane foam production, resulting in defective foam after prolonged use. Patent CN101503566B disclosed a polyether containing urethane or urea groups, which can be used as a compatibilizer to improve the storage stability of polyols.

[0004] As is well known, silicone oil can be used as a foam stabilizer in the synthesis of polyurethane foam. Foam stabilizers play roles in emulsification, promoting bubble nucleation, and stabilizing bubbles during the polyurethane foaming process. The typical structure of polyurethane foam stabilizers is a Si-C type with side chains, usually prepared by hydrosilylation of hydrogen-containing polysiloxanes with allyl polyoxyethylene polyoxypropylene ethers. The polysiloxane, as a hydrophobic segment, reduces the surface tension of the system, while the hydrophilic polyoxyethylene and hydrophobic polyoxypropylene segments in the modified structure increase the compatibility of the composite material. A well-formed foam stabilizer possesses both the solubility required for an excellent emulsifier and the ability to reduce surface tension and stabilize bubbles through the Marangoni-Gibbs effect, essential for an excellent nucleating agent. Patent CN115819780B provides a polyether-modified silicone oil and its preparation method, which can improve the compatibility of the composite material with cyclopentane, improve surface defects in polyurethane foam, and reduce the number of surface bubbles. Although existing silicone oil structural designs can improve the compatibility between composite materials to some extent, no silicone oil can currently improve the storage stability of heterogeneous composite materials (isocyanate reactive components) caused by polyol incompatibility.

[0005] Therefore, the polyether-modified silicone oil provided by the present invention simultaneously functions as a foam stabilizer and a polyol compatibilizer. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a polyether-modified silicone oil with higher controllability and better chemical stability, as well as its preparation method, which combines the functions of a foam stabilizer and a polyol compatibilizer. Through structural design, this invention prepares ordinary polyether and alkyl polyether-modified silicone oils. This silicone oil utilizes the combination of hydrophilic and hydrophobic segments in its structure to improve the compatibility of immiscible polyol compositions and increase the storage stability of isocyanate reactive compounds. Simultaneously, it effectively generates the Marangoni-Gibbs effect during polyurethane foam formation, giving the bubbles both "instantaneous" and sustained stability, thereby obtaining polyurethane foams with stable production, good surface condition, and fine pores.

[0007] The present invention also provides a polyurethane foam composition, which has the advantages of stable production, good surface condition and fine cell structure.

[0008] To achieve the above-mentioned objectives, the technical solution of this invention is as follows:

[0009] A polyether-modified silicone oil, characterized in that its silicone oil structure simultaneously contains the following segments:

[0010] (a) Polyoxyethylene ether segments;

[0011] (b) Alkylated polyoxyethylene polyoxypropylene ether segments, where EO and PO can be random copolymers or block copolymers;

[0012] The molar ratio of polyoxyethylene ether segments to alkylated polyoxyethylene polyoxypropylene ether segments is 1:0.6 to 4, preferably 1:1 to 2.

[0013] The polyether-modified silicone oil is prepared by reacting components comprising the following:

[0014] (I) Allyl polyoxyethylene polyoxypropylene ether component, wherein the structure of the allyl polyoxyethylene polyoxypropylene ether is:

[0015]

[0016] Where the repeating units a are 1 to 25, b are 2 to 25, and b ≥ a;

[0017] (II) Allyl polyoxyethylene ether component, wherein the allyl polyoxyethylene ether has the following structure:

[0018]

[0019] The repeating unit c ranges from 3 to 50;

[0020] (III) Hydrogen-containing silicone oil component, wherein the structure of the hydrogen-containing silicone oil is:

[0021]

[0022] The repeating units m and n are 5 to 15;

[0023] (IV) Alkyl end-capping agent components;

[0024] (V) Catalyst components, the catalyst components including catalyst 1, which is capable of catalyzing the reaction of polyether terminal hydroxyl groups with alkyl end-capping agents, and catalyst 2, which is capable of catalyzing the reaction of double bonds and silane-hydrogen bonds.

[0025] The alkyl end-capping agent component is a haloalkane with the structure RX, wherein R is a C1-4 alkyl group, preferably methyl or n-butyl; and X is a halogen atom, preferably Cl or Br atom.

[0026] The catalyst 1 is an alkaline catalyst. Preferably, the catalyst is a hydroxide, and more preferably, the catalyst is potassium hydroxide or sodium tert-butoxide.

[0027] The catalyst 2 is a platinum catalyst, a rhodium catalyst, or a palladium catalyst, preferably chloroplatinic acid.

[0028] The preparation method of the polyether-modified silicone oil includes the following steps:

[0029] 1) Allyl polyoxyethylene polyoxypropylene ether first undergoes an activation reaction in the presence of catalyst 1, and then undergoes an alkylation reaction with an alkyl end-capping agent to generate alkyl-terminated allyl polyoxyethylene polyoxypropylene ether.

[0030] 2) Hydrogen-containing silicone oil, allyl polyoxyethylene ether, and alkyl-terminated allyl polyoxyethylene polyoxypropylene ether are reacted under the action of catalyst 2 to prepare polyether-modified silicone oil.

[0031] The molar ratio of the allyl polyoxyethylene polyoxypropylene ether to catalyst 1 is 1:1.5 to 2.

[0032] The molar ratio of the allyl polyoxyethylene polyoxypropylene ether to the alkyl end-capping agent is 1:1.2 to 2.5.

[0033] The molar ratio of the silicon-hydrogen bonds in the hydrogen-containing silicone oil to the vinyl substances in the alkyl-terminated allyl polyoxyethylene polyoxypropylene ether and allyl polyoxyethylene ether [n(Si-H):n(C=C)] is 1:1 to 1.5, preferably 1:1.1 to 1.2.

[0034] The catalyst 2 is added in an amount of 0.001% to 0.2 wt.%, calculated based on a total weight of 100 wt.% for hydrogen-containing silicone oil, allyl polyoxyethylene ether, and alkyl-terminated allyl polyoxyethylene polyoxypropylene ether.

[0035] In step 1), the activation reaction temperature is 20–135°C, and the activation time is 1–2 h. The alkylation reaction temperature is 20–60°C, and the alkylation time is 4–8 h. In step 2), the reaction temperature is 100–120°C, and the reaction time is 4–10 h.

[0036] All of the reactions occurred in a nitrogen atmosphere.

[0037] In some specific implementations, step 1) employs a solid-state catalytic system. More specifically, the solid-state catalytic reaction system refers to adding allyl polyoxyethylene polyoxypropylene ether, a solid catalyst, and a dehydrating agent to a four-necked flask, purging with nitrogen for several minutes under stirring, and reacting at 25°C or 90–110°C for 1–3 hours. Then, a certain amount of haloalkanes is added dropwise. After the addition is complete, the reaction continues at 25°C or 50°C for 4–8 hours to obtain a crude product. Distilled water and phosphoric acid are added to the crude product for washing and neutralization, stirring at 80–90°C for 1 hour, then maintaining the temperature at 70–90°C to allow the reactants to separate into layers. The aqueous phase is removed, and the product is dehydrated under vacuum. The filtered liquid is the end-capped polyether product.

[0038] The weight ratio of the solid catalyst to the dehydrating agent is 1:1 to 3.

[0039] In some specific embodiments, the dehydrating agent is preferably calcium oxide.

[0040] In some specific implementations, step 1) employs an aqueous catalytic system. More specifically, the aqueous catalytic reaction system refers to adding a measured amount of allyl polyoxyethylene polyoxypropylene ether, 50-80 wt.% aqueous hydroxide solution, and an antioxidant to a four-necked flask. Under stirring, the mixture is fully purged with nitrogen while simultaneously dehydrating under reduced pressure, and the temperature is raised to 110°C-130°C. After dehydration is complete, the reaction proceeds for a period of time, then the temperature is lowered to 50°C, and a measured amount of halobutane is added dropwise. After the addition is complete, the reaction continues for 4-8 hours to obtain a crude product. Distilled water and phosphoric acid are added to the crude product for washing and neutralization. The mixture is stirred at 80-90°C for 1 hour, then maintained at 70-90°C to allow the reactants to separate into layers. The aqueous phase is removed, and the mixture is dehydrated under vacuum. The filtered liquid is the end-capped polyether product.

[0041] The antioxidant is 2% to 5% of the mass of the polyether.

[0042] In some specific embodiments, the antioxidant is preferably anhydrous sodium sulfate.

[0043] In another aspect of the present invention, the aforementioned polyether-modified silicone oil can be used in polyurethane foam compositions.

[0044] A polyurethane foam composition is obtained by reacting isocyanate reactive component A and isocyanate component B. The isocyanate reactive component A includes, but is not limited to, polyols, catalysts, blowing agents, polyether-modified silicone oils, and optionally chain extenders and flame retardants. The polyether-modified silicone oil is prepared by the aforementioned method or is a polyether-modified silicone oil as described above.

[0045] The polyether-modified silicone oil of the present invention is particularly preferred for use in white materials containing polyols of different structures and polarities, because these polyols typically tend to separate after mixing.

[0046] In a specific embodiment, the polyol in the isocyanate reactive component A includes at least two incompatible polyether polyols, A1 and A2; wherein, polyether polyol A1 has a functionality of 2-5, preferably 3-5, a hydroxyl value of 250-800 mgKOH / g, and an EO content of 40-100 wt.% in its molecular structure; and polyol A2 has a functionality of 2-8, a hydroxyl value of 20-600 mgKOH / g, and an EO content of 0-20 wt.% in its molecular structure.

[0047] In a specific embodiment, based on the total mass of the isocyanate reactive component A, the isocyanate reactive component comprises:

[0048] Polyether polyol A1, in an amount of 25-90%, preferably 35-80%, more preferably 40-75%;

[0049] Polyol A2, used in an amount of 5-45%, preferably 15-35%, more preferably 20-30%;

[0050] Catalyst A3, used in an amount of 0.01–1%, preferably 0.01–0.1%;

[0051] Foaming agent A4, used in an amount of 0.1-2%, preferably 0.5-1%;

[0052] Polyether-modified silicone oil, used in amounts of 0.5-10%, preferably 1-5%;

[0053] Flame retardant A5, used in an amount of 0-50%, preferably 5-30%, more preferably 10-20%;

[0054] Chain extender A6 is used in an amount of 0-30%, preferably 5-15%, and more preferably 8-10%.

[0055] More specifically, the polyether polyol A1 is mainly obtained by chemically reacting water and / or polyol as initiators and EO and / or PO as polymerization monomers under the action of a catalyst to obtain a class of compounds, wherein the proportion of EO in the molecular structure is 40-100 wt.%, preferably 50-100 wt.%, and the polymerization structure of EO and PO can be block or random. The initiator includes, but is not limited to, water, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, pentanediol, hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, diethylene glycol, neopentanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A, bisphenol S, or mixtures thereof, preferably difunctional small molecule alcohols containing active hydrogen such as propylene glycol or dipropylene glycol, or trifunctional small molecule alcohols containing active hydrogen such as glycerol or trimethylolpropane; the catalyst includes, but is not limited to, basic hydroxides, basic alkoxides, antimony pentachloride, or mixtures thereof.

[0056] The polyol A2 may optionally include polyether polyols, polyester polyols, polycarbonate polyols, bio-based polyols, etc. These compounds may be used alone or in combination without affecting the implementation of the present invention.

[0057] The catalyst A3 includes, but is not limited to, thermosensitive or temperature-sensitive, delayed catalysts. More preferably, the A3 catalyst includes, but is not limited to, triethylenediamine, pentamethyldialkyltriamine, tetramethylalkyldiamine, bis(dimethylaminoethyl) ether, cyclohexylmethyl tertiary amine, stannous octoate, stannous oleate, stannous laurate, dimethyl dilaurate, dibutyl dilaurate, dibutyl dithiol tin, bismuth octoate, bismuth neodecanoate, bismuth naphthenate, or combinations thereof.

[0058] The foaming agent A4 is added to the polyurethane foam material to make the polyurethane porous, including but not limited to physical and chemical foaming agents. Preferably, the foaming agent A6 is water.

[0059] The flame retardant enables the polyurethane foam material obtained from the reaction to have a flame retardant effect. Preferably, the flame retardant A5 is a liquid flame retardant with a viscosity of 1 to 2000 mPa·s at 25°C. More preferably, the liquid flame retardant A5 has a viscosity of 60 to 500 mPa·s at 25°C. Preferred examples include, but are not limited to, tris(2-chloroethyl) phosphate, tris(2,3-dichloropropyl) phosphate, dimethyl methyl phosphate, tris(2-chloropropyl) phosphate, tricresyl phosphate, diphenyl toluene phosphate, or combinations thereof.

[0060] Preferably, the chain extender A6 is a polyhydroxy compound with a terminal -OH group and a functionality of 1-4, preferably 2-3, including but not limited to glycerol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, diethylene glycol, dipropylene glycol, methylpropylene glycol, 1,4-butanediol, 1,3-butanediol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-cyclohexanol, 1,6-hexanediol, diethanolamine, triethanolamine, triisopropanolamine, or combinations thereof. More preferably, the chain extender A5 is selected from ethylene glycol, propylene glycol, glycerol, trimethylolpropane, or combinations thereof.

[0061] In a specific embodiment, the NCO content of the isocyanate component B is 20-50 wt.%, and the viscosity at 25°C is 1-5000 mPa·s.

[0062] The isocyanate component B is selected from one or a mixture of organic isocyanate monomers, isocyanate prepolymers, polyisocyanates, and isocyanate modified products, and the functionality of the isocyanate component is 2 to 5.

[0063] In some embodiments of the method according to the present invention, the isocyanate component B includes, but is not limited to, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), naphthalene diisocyanate (NDI), terephthalic diisocyanate (PPDI), 1,4-cyclohexane diisocyanate (CHDI), phenylenediamine diisocyanate (XDI), cyclohexane diisocyanate (HXDI), trimethyl-1,6-hexamethylene diisocyanate (TMHDI), and tetramethyl-m-phenylenediamine diisocyanate. Isocyanates (TMXDI), norbornene diisocyanate (NBDI), dimethylbiphenyl diisocyanate (TODI), methylcyclohexyl diisocyanate (HTDI), tetramethylene diisocyanate, pentamethylene diisocyanate, 2,4,6-trimethyl-1,3-phenyl diisocyanate, 4-chloro-6-methyl-1,3-phenyl diisocyanate, poly(tetrafluoroethylene oxide-co-difluoromethyleneoxy)α,ω-diisocyanate, 1,4-butane diisocyanate, 1,8-octane diisocyanate, 1,3-bis(1-isocyanate-1-methylethyl)benzene, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, naphthalene-1,5-diisocyanate, 1,3-benzene Diisocyanate, 1,4-phenyl diisocyanate, 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures of these isomers, terephthalimide diisocyanate, and at least one of the prepolymers or modified products of the above isocyanates, preferably toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), naphthalene diisocyanate (NDI), terephthalimide diisocyanate (PPDI), 1,4-cyclohexane diisocyanate (CHDI), terephthalimide diisocyanate (X The isocyanate is at least one of the following: di(II), cyclohexanedimethyl diisocyanate (HXDI), trimethyl-1,6-hexamethylene diisocyanate (TMHDI), tetramethyl-isophthalamide diisocyanate (TMXDI), norbornane diisocyanate (NBDI), dimethyl biphenyl diisocyanate (TODI), methylcyclohexyl diisocyanate (HTDI), and prepolymers or modified products of the above isocyanates; more preferably, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and prepolymers or modified products of the above isocyanates.

[0064] In this invention, the number of molar hydrogen atoms of the active hydrogen in the isocyanate reactive component A is 'a', the number of molar isocyanate groups in the isocyanate component B is 'b', and the isocyanate index R = b / a = 0.8–2. In some embodiments of the method according to this invention, 1–1.2 is preferred. It should be noted that the active hydrogen atom refers to a hydrogen atom capable of reacting with the isocyanate group.

[0065] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0066] This invention provides a polyether-modified silicone oil and a polyurethane foam composition containing the same. The polyether-modified silicone oil acts as both a foam stabilizer and a polyol compatibilizer, which not only improves the long-term storage stability of isocyanate reactive materials, but also produces polyurethane foam with stable production and good surface condition, achieving technical effects that existing silicone oils cannot achieve.

[0067] The polyether-modified silicone oil is produced by modifying hydrogen-containing silicone oil with ordinary polyoxyethylene ether and alkyl-terminated polyoxyethylene polyoxypropylene ether. The alkylation of the polyoxyethylene polyoxypropylene ether imparts better oleophilicity and chemical stability, improving the quality and effective components of the modified product. Meanwhile, the polyoxyethylene ether contains more hydrophilic molecular segments. The combination of hydrophilic and hydrophobic segments in the molecular structure improves the compatibility of immiscible polyol compositions and increases the storage stability of isocyanate reactive components in the foam composition. Simultaneously, the silicone oil described in this invention possesses hydrophobic polysiloxane segments, which effectively reduce surface tension. Furthermore, due to its excellent emulsifying effect, it can effectively generate the Marangoni-Gibbs effect during polyurethane foam formation, giving the bubbles both "instantaneous" and sustained stability, thus obtaining polyurethane foam with stable production and good surface condition. The resulting polyurethane foam composition exhibits excellent raw material storage stability and foam production stability, reducing production costs and fluctuations, making it more suitable for industrial applications. Detailed Implementation

[0068] The present invention will be further described in detail below through specific embodiments, but it should not be construed as limiting the scope of the invention to the following examples. Various substitutions or modifications made based on ordinary technical knowledge and conventional methods in the art without departing from the above-described methodological spirit of the invention should be included within the scope of the invention. In this application, parts and percentages are generally by weight, unless otherwise specified.

[0069] Main raw material sources

[0070] Allyl polyoxyethylene polyoxypropylene ether 1, EO / PO repeating unit is 10 / 10, industrial grade, Haian Petrochemical Plant, Jiangsu Province.

[0071] Allyl polyoxyethylene polyoxypropylene ether 2, EO / PO repeating unit is 1 / 25, industrial grade, Haian Petrochemical Plant, Jiangsu Province.

[0072] Allyl polyoxyethylene ether APEG-580, with a molecular weight of 580, is manufactured by Wuhan Pushida Biotechnology Co., Ltd.

[0073] Allyl polyoxyethylene ether APEG-800, with a molecular weight of 800, is manufactured by Wuhan Pushida Biotechnology Co., Ltd.

[0074] Allyl polyoxyethylene ether APEG-1100, with a molecular weight of 1100, is manufactured by Wuhan Pushida Biotechnology Co., Ltd.

[0075] Hydrogen-containing silicone oil 1, molecular weight 1100, activated hydrogen mass fraction 0.64%, Jiangsu Keqi Polymer Materials Research Institute Co., Ltd.

[0076] Hydrogen-containing silicone oil 2, molecular weight 1400, activated hydrogen mass fraction 0.86%, Jiangsu Keqi Polymer Materials Research Institute Co., Ltd.

[0077] Sodium tert-butoxide (t-BuONa): Analytical grade, Sinopharm Chemical Reagent Co., Ltd.

[0078] Potassium hydroxide (KOH): Analytical grade, Sinopharm Chemical Reagent Co., Ltd.

[0079] Bromoethane: Chemically pure, Sinopharm Chemical Reagent Co., Ltd.

[0080] Iodomethane: Chemically pure, Sinopharm Chemical Reagent Co., Ltd.

[0081] Calcium oxide: analytical grade, Sinopharm Chemical Reagent Co., Ltd.

[0082] Anhydrous sodium sulfate, analytical grade, Sinopharm Chemical Reagent Co., Ltd.

[0083] Polyether polyol 1-1, glycerol-initiated, EO polymerized, hydroxyl value 600 mg KOH / g, EO content 100 wt.%, Jiangsu Zhongshan Chemical Co., Ltd.

[0084] Polyether polyol 1-2, glycerol starting material, copolymer of EO and PO, hydroxyl value 400mgKOH / g, EO content 40wt.%, Wanhua Chemical;

[0085] Polyol 2-1, castor oil polyol, hydroxyl value 163mgKOH / g, EO content 0wt.%, Fucheng County Huanyu Oil Factory;

[0086] Polyol 2-2, polyether polyol, glycerol-initiated, PO polymerized, hydroxyl value 240 mg KOH / g, EO content 0 wt.%, Dexin Federal Chemical Industry Co., Ltd.

[0087] Polyol 2-3, polyether polyol, glycerol starting material, copolymer of EO and PO, hydroxyl value 168mgKOH / g, EO content 20wt.%, Wanhua Chemical;

[0088] Catalyst: KC152, Wanhua Chemical;

[0089] Flame retardant: Tris(2-chloropropyl) phosphate, Anhui Runyue;

[0090] Chain extender: DEG, Wuxi Chemical Additives Factory;

[0091] Foaming agent: water.

[0092] Polyether-modified silicone oil 1, prepared as described in the example.

[0093] Polyether-modified silicone oil 2, prepared as described in the example.

[0094] Polyether-modified silicone oil 3, prepared as described in the example.

[0095] Silicone Oil 4: A mixture of polydimethyl silicone oil and polyether, wherein the polyether EO / PO mass ratio is 1 / 0.9, Evonik.

[0096] Silicone Oil 5: Polyether-modified silicone oil with an EO / PO mass ratio of 35 / 65, made by Meiside.

[0097] Silicone Oil 6: Polyether-modified silicone oil with an EO / PO mass ratio of 75 / 25, Evonik.

[0098] Isocyanate component (B): WANNATE 9043, NCO content 31.2wt%, viscosity at 25℃ 200mPa·s, Wanhua Chemical.

[0099] Main testing methods

[0100] Method for testing the storage stability of component A of the polyurethane foam composition: Mix component A thoroughly according to the dosage of each component, then take 40g of raw material and place it in a 60mL transparent sample bottle (diameter 27.5mm, height 140mm), and store it in a constant temperature incubator at 25 / 40℃. The stability is visually measured at the following intervals: 2h, 4h, 8h, 16h, 24h, 36h, 48h, and then measured every 24h thereafter, with the longest storage experiment being 720h; if phase separation occurs in 1mL of component A in the sample bottle, it is determined to be storage stratification.

[0101] Methods for testing the foaming stability and production stability of polyurethane foam compositions:

[0102] (1) Manual free foaming: According to the types and amounts of each component in Table 1, component A is mixed uniformly in advance according to the amount of each component. Then, components A and B, both with a material temperature of 25℃, are mixed uniformly. Take 80g and pour it into a 500mL paper cup. The foaming stability characterization method is to observe whether there is a tendency to collapse during the foaming process and record the surface state of the foam and the pore size of the cells after curing.

[0103] (2) High-Pressure Press Free Bubbling: The high-pressure press described in Table 3 was used for mixing AB materials. Before loading the press, component A was pre-mixed evenly according to the dosage of each component, and then loaded into the press tank. The stirring of component A was turned on, and internal circulation (components A and B circulated in their respective tanks and pipelines) was performed for 1 hour. 80g of the AB mixture was discharged into a 500mL paper cup. The foaming stability characterization method was to observe whether there was a tendency for foam collapse during the foaming process and record the pore size of the cells after curing. The injection pressure was 100 bar, the mixing flow rate was 150g / s, and the material temperature was 25℃. The production stability characterization method was to compare whether there was a tendency for foam collapse during the foaming process when the AB mixture was discharged after pre-mixing component A and after 1 hour and 72 hours of internal circulation in the high-pressure press, and record the surface state of the foam and the pore size of the cells after curing.

[0104] Examples and Comparative Examples

[0105] The polyether-modified silicone oil preparation method used in the examples is as follows:

[0106] Preparation of polyether-modified silicone oil 1:

[0107] 1) Preparation of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 1: 100g of allyl polyoxyethylene polyoxypropylene ether 1 and 18g of t-BuONa were added to a 250mL four-necked flask. The mixture was purged with nitrogen for several minutes with stirring and reacted at 25℃ for 2 hours. Then, 24g of iodomethane was added dropwise at 25℃. After the addition was complete, the reaction continued for 4 hours to obtain the crude product. Appropriate amounts of distilled water and phosphoric acid were added to the crude product for washing and neutralization. The pH was adjusted to 6, and the mixture was stirred at 80–90℃ for 1 hour. The temperature was then maintained at 70–90℃ to allow the reactants to separate into layers. The aqueous phase was removed, and the mixture was dehydrated under vacuum. The filtered liquid was the end-terminated polyether product.

[0108] 2) Preparation of polyether-modified silicone oil 1: 20g of hydrogen-containing silicone oil 1, 85g of APEG-1100, and 83g of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 1 were added to a 500mL three-necked flask, along with 0.05wt% of chloroplatinic acid as a catalyst. The mixture was reacted at 100℃ for 8 hours under nitrogen protection. After the reaction was completed, the product was rotary evaporated to remove a small amount of low-boiling substances, thus obtaining polyether-modified silicone oil 1.

[0109] Preparation of polyether-modified silicone oil 2:

[0110] 1) Preparation of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 2: 100g of allyl polyoxyethylene polyoxypropylene ether 1, 10g of 80wt.% KOH aqueous solution, and 2g of anhydrous sodium sulfite antioxidant were added to a four-necked flask. The mixture was thoroughly purged with nitrogen under stirring, while simultaneously dehydrating under reduced pressure, and heated to 130℃. After dehydration, the reaction was allowed to proceed for 1 hour, then cooled to 50℃ and 12.5g of bromoethane was added dropwise. After the addition was complete, the reaction continued for 4.5 hours to obtain the crude product. Appropriate amounts of distilled water and phosphoric acid were added to the crude product for washing and neutralization, adjusting the pH to 6. The mixture was stirred at 80–90℃ for 1 hour, then maintained at 70–90℃ to allow the reactants to separate into layers. The aqueous phase was removed, and the mixture was dehydrated under vacuum. The filtered liquid was the end-terminated polyether product.

[0111] 2) Preparation of polyether-modified silicone oil 2: 20g of hydrogen-containing silicone oil 1, 64g of APEG-800, and 52.5g of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 2 were added to a 500mL three-necked flask. Simultaneously, 0.05wt% of chloroplatinic acid catalyst was added, and the mixture was reacted at 100℃ for 8 hours under nitrogen protection. After the reaction was complete, the product was rotary evaporated to remove a small amount of low-boiling-point substances, yielding polyether-modified silicone oil 2.

[0112] Preparation of polyether-modified silicone oil 3:

[0113] 1) Preparation of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 3: 200g of allyl polyoxyethylene polyoxypropylene ether 2, 13g of KOH, and 200g of calcium oxide (a desiccant) were added to a 1000mL four-necked flask. The mixture was purged with nitrogen for several minutes with stirring and reacted at 105℃ for 1 hour. The temperature was then lowered to 50℃, and 35.4g of bromoethane was added dropwise. After the addition was complete, the reaction continued for 7.5 hours to obtain the crude product. Appropriate amounts of distilled water and phosphoric acid were added to the crude product for washing and neutralization. The pH was adjusted to 6, and the mixture was stirred at 80–90℃ for 1 hour. The temperature was then maintained at 70–90℃ to allow the reactants to separate into layers. The aqueous phase was removed, and the mixture was dehydrated under vacuum. The filtered liquid was the end-terminated polyether product.

[0114] 2) Preparation of polyether-modified silicone oil 3: 10g of hydrogen-containing silicone oil 2, 15g of APEG-580, and 160g of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 3 were added to a 500mL three-necked flask, along with 0.1wt% of chloroplatinic acid as a catalyst. The reaction was carried out at 100℃ for 8 hours under nitrogen protection. After the reaction was completed, the product was rotary evaporated to remove a small amount of low-boiling substances, thus obtaining polyether-modified silicone oil 3.

[0115] The amounts of each component in the polyurethane foam compositions of the examples and comparative examples are listed in Table 1. Component A is obtained by uniformly mixing polyol, KC152, water, tris(2-chloropropyl)phosphate, DEG, and silicone oil according to the proportions shown in the table below. The mass ratio of components A and B is calculated based on the isocyanate index, and then the two are mixed uniformly to react and foam, thus obtaining polyurethane foam.

[0116] Table 1. Amounts (parts by mass) of each component in the examples and comparative examples of polyurethane foam compositions.

[0117]

[0118] Table 2. Separation time of component A at 40°C in the examples and comparative examples.

[0119]

[0120] Table 3 Specific parameters of high-pressure equipment

[0121]

[0122] Table 4. Free bubble stability in the examples and comparative examples.

[0123]

[0124]

[0125]

[0126] As can be seen from the test results in the table above, the polyether-modified silicone oil described in this invention, compared with existing silicone oils, can not only improve the storage stability of the polyol in the isocyanate reactive component A of the polyurethane foam composition, but also obtain polyurethane foam with stable foaming process, stable production, good surface condition and fine cell structure when used on the machine for a long time.

[0127] It is readily understood that the above embodiments are merely illustrative examples for clear explanation and do not imply that the invention is limited thereto. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A polyether-modified silicone oil, characterized in that, Its silicone oil structure contains the following segments: (a) Polyoxyethylene ether segments; (b) Alkylated polyoxyethylene polyoxypropylene ether segments, where EO and PO are random copolymers or block copolymers; The molar ratio of polyoxyethylene ether segments to alkylated polyoxyethylene polyoxypropylene ether segments is 1:0.6~4. The preparation method of the polyether-modified silicone oil includes the following steps: Step 1) Allyl polyoxyethylene polyoxypropylene ether first undergoes an activation reaction in the presence of catalyst 1, and then undergoes an alkylation reaction with an alkyl end-capping agent to generate alkyl-terminated allyl polyoxyethylene polyoxypropylene ether. Step 2) Hydrogen-containing silicone oil, allyl polyoxyethylene ether, and alkyl-terminated allyl polyoxyethylene polyoxypropylene ether react under the action of catalyst 2 to prepare polyether-modified silicone oil; The structure of the allyl polyoxyethylene polyoxypropylene ether is as follows: Where the repeating units a are 1~25, b are 2~25, and b≥a.

2. The polyether-modified silicone oil as described in claim 1, characterized in that, The molar ratio of polyoxyethylene ether segments to alkylated polyoxyethylene polyoxypropylene ether segments is 1:1~2.

3. The polyether-modified silicone oil as described in claim 1, characterized in that, It is prepared by reacting the following components: Component (I) Allyl polyoxyethylene polyoxypropylene ether component, wherein the structure of the allyl polyoxyethylene polyoxypropylene ether is as follows: Where the repeating units a are 1~25, b are 2~25, and b≥a; Component (II) Allyl polyoxyethylene ether component, wherein the structure of the allyl polyoxyethylene ether is: The repeating unit c is 3~50; Component (III) is a hydrogen-containing silicone oil component, wherein the structure of the hydrogen-containing silicone oil is as follows: The repeating units m and n are 5 to 15; Component (IV) Alkyl end-capping agent component; Component (V) Catalyst component, wherein the catalyst component includes catalyst 1, which is capable of catalyzing the reaction of polyether terminal hydroxyl groups with alkyl end-capping agents, and catalyst 2, which is capable of catalyzing the reaction of double bonds and silane-hydrogen bonds.

4. The polyether-modified silicone oil according to any one of claims 1 to 3, characterized in that, The alkyl end-capping agent component is a haloalkane with the structure RX, where R is a C1~4 alkyl group and X is a halogen atom.

5. The polyether-modified silicone oil as described in claim 4, characterized in that, R is methyl or n-butyl; X is a Cl or Br atom.

6. The polyether-modified silicone oil according to any one of claims 1 to 3, characterized in that, Catalyst 1 is an alkaline catalyst; catalyst 2 is a platinum catalyst, rhodium catalyst, or palladium catalyst.

7. The polyether-modified silicone oil according to claim 6, characterized in that, The catalyst 1 is a hydroxide; the catalyst 2 is chloroplatinic acid.

8. A method for preparing the polyether-modified silicone oil according to any one of claims 1 to 7, comprising the following steps: Step 1) Allyl polyoxyethylene polyoxypropylene ether first undergoes an activation reaction in the presence of catalyst 1, and then undergoes an alkylation reaction with an alkyl end-capping agent to generate alkyl-terminated allyl polyoxyethylene polyoxypropylene ether. Step 2) Hydrogen-containing silicone oil, allyl polyoxyethylene ether, and alkyl-terminated allyl polyoxyethylene polyoxypropylene ether react under the action of catalyst 2 to prepare polyether-modified silicone oil.

9. The preparation method according to claim 8, characterized in that, The molar ratio of the allyl polyoxyethylene polyoxypropylene ether to catalyst 1 is 1:1.5~2; and / or, The molar ratio of the allyl polyoxyethylene polyoxypropylene ether to the alkyl end-capping agent is 1:1.2~2.5; and / or, The molar ratio of the silicon-hydrogen bonds in the hydrogen-containing silicone oil to the vinyl groups in the alkyl-terminated allyl polyoxyethylene polyoxypropylene ether and allyl polyoxyethylene ether [n(Si-H):n(C=C)] is 1:1~1.5; and / or, The catalyst 2 is added in an amount of 0.001% to 0.2 wt.%, calculated based on a total weight of 100 wt.% for hydrogen-containing silicone oil, allyl polyoxyethylene ether, and alkyl-terminated allyl polyoxyethylene polyoxypropylene ether.

10. The preparation method according to claim 9, characterized in that, The ratio of the amount of silicon-hydrogen bonds in the hydrogen-containing silicone oil to the amount of vinyl substances in the alkyl-terminated allyl polyoxyethylene polyoxypropylene ether and allyl polyoxyethylene ether [n(Si-H):n(C=C)] is 1:1.1~1.

2.

11. The preparation method according to any one of claims 8-10, characterized in that, The activation reaction temperature in step 1) is 20~135℃ and the activation time is 1~2h; and / or, the alkylation reaction temperature is 20~60℃ and the alkylation time is 4~8h; and / or, the reaction temperature in step 2) is 100~120℃ and the reaction time is 4~10h.

12. The preparation method according to any one of claims 8-10, characterized in that, All of the reactions occurred in a nitrogen atmosphere.

13. A polyurethane foam composition, characterized in that, It is obtained by reacting isocyanate reactive component A and isocyanate component B, wherein the isocyanate reactive component A includes a polyol, a catalyst, a foaming agent, a polyether-modified silicone oil, an optional chain extender and a flame retardant; wherein the polyether-modified silicone oil is the polyether-modified silicone oil according to any one of claims 1-7, or the polyether-modified silicone oil prepared by the method according to any one of claims 8-12.

14. The polyurethane foam composition according to claim 13, characterized in that, The polyol in the isocyanate reactive component A includes at least two incompatible polyether polyols, A1 and A2; wherein, polyether polyol A1 has a functionality of 2-5, a hydroxyl value of 250-800 mgKOH / g, and an EO content of 40-100 wt.% in its molecular structure; and polyol A2 has a functionality of 2-8, a hydroxyl value of 20-600 mgKOH / g, and an EO content of 0-20 wt.% in its molecular structure.

15. The polyurethane foam composition of claim 14, characterized in that, The functionality of polyether polyol A1 is 3~5.

16. The polyurethane foam composition of claim 14, characterized in that, Based on the total mass of the isocyanate reactive component A, it comprises: Polyether polyol A1, used in amounts of 25-90%; Polyol A2, used in amounts of 5-45%; Catalyst, dosage: 0.01~1%; Polyether-modified silicone oil, used in amounts of 0.5-10%; Foaming agent, dosage: 0.1-2%; Flame retardant, dosage 0-50%; Chain extender, dosage 0~30%.

17. The polyurethane foam composition of claim 16, characterized in that, Based on the total mass of the isocyanate reactive component A, it comprises: Polyether polyol A1, used in amounts of 35-80%; Polyol A2, used in amounts of 15-35%; Catalyst, dosage: 0.01~0.1%; Polyether-modified silicone oil, used at a dosage of 1-5%; Foaming agent, dosage: 0.5-1%; Flame retardant, dosage 5-30%; Chain extender, dosage 5-15%.

18. The polyurethane foam composition of claim 16, characterized in that, Based on the total mass of the isocyanate reactive component A, Polyether polyol A1, used in amounts of 40-75%; Polyol A2, used in amounts of 20-30%; Flame retardant, dosage: 10-20%; Chain extender, dosage 8-10%.

19. The polyurethane foam composition according to any one of claims 13 to 18, characterized in that, The isocyanate component B has an NCO content of 20~50 wt.% and a viscosity of 1~5000 mPa·s at 25°C.

20. The polyurethane foam composition of claim 19, characterized in that, The isocyanate index R = 0.8~2.

21. The polyurethane foam composition of claim 20, characterized in that, The isocyanate index R = 1~1.2.

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