Polyether modified silicone oil, preparation method thereof and polyurethane foam composition

Abstract

The invention discloses polyether modified silicone oil for improving polyol compatibility and application of the polyether modified silicone oil in a polyurethane foam composition. The structure of the polyether modified silicone oil simultaneously comprises the following chain segments: (a) a polyoxyethylene ether chain segment; and (b) alkylated polyoxyethylene polyoxypropylene ether chain segments, wherein EO and PO can be random copolymerization or block copolymerization. Wherein the molar ratio of the polyoxyethylene ether chain segment to the alkylated polyoxyethylene polyoxypropylene ether chain segment is 1: (0.6-4), preferably 1: (1-2). The polyurethane composition comprises a component A and a component B, the component A is an isocyanate reactive component and comprises polyol, a catalyst, a foaming agent and polyether modified silicone oil; and the component B is an isocyanate component. The polyether modified silicone oil has the functions of a compatilizer and a foam stabilizer, and a polyurethane composition has good storage performance and foaming stability and can be used for preparing a polyurethane foaming material.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane foam material preparation, and more specifically to a polyether-modified silicone oil for improving the compatibility of polyols and a preparation method thereof, which can be applied to polyurethane foam compositions. Background Art

[0002] Polyurethane has the properties of foamability, high adhesion, high elasticity and insulation, and can be used to make various products. It is the only organic polymer material among polymer materials that is widely used in the fields of foam, plastic and coating. As one of the most widely used polyurethane products, polyurethane foam has many excellent properties and plays an indispensable role in life.

[0003] At present, polyurethane foam is mostly prepared by a one-step method, that is, isocyanate reactive components (such as polyols, blowing agents, catalysts, surfactants) and isocyanates are reacted and foamed. Wherein, polyol mixture reacts with isocyanates as an active part, and therefore, a large part of the performance of polyurethane foam depends on the composition and structure of polyol mixture. In the industrial production of polyurethane foam, different types of polyols are often used, but different types of polyols may have certain incompatibility due to differences in structure, molecular weight, etc., and the compatibility of polyols not only directly affects the stability of polyol mixture storage, but also causes the instability of polyurethane foam production, resulting in defective foams when used for a long time. Patent CN101503566B once disclosed a polyether containing carbamate or urea group, 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 and is widely used in the synthesis of polyurethane foam. In the process of polyurethane foaming, foam stabilizers play the role of emulsification, promoting bubble nucleation, and stabilizing foam. The typical structure of polyurethane foam stabilizers is Si-C side chain type, usually prepared by hydrogen-containing polysiloxane and allyl polyoxyethylene polyoxypropylene ether through silylation reaction, wherein polysiloxane as a hydrophobic segment can reduce the surface tension of the system, and the hydrophilic polyoxyethylene segment and hydrophobic polyoxypropylene segment in the modified structure increase the compatibility of the combined material. The foam stabilizer with suitable composition has both the solubility required as an excellent emulsifier and the ability to reduce surface tension and stabilize bubbles through the Marangoni-Gibbs effect as an excellent nucleating agent. Patent CN115819780B provides a polyether-modified silicone oil and a preparation method thereof, which can improve the compatibility of the combined material with cyclopentane, improve the surface defects of polyurethane foam, and reduce the number of surface bubbles. Although the existing silicone oil structure design can improve the compatibility between the combined materials to a certain extent, there is currently no silicone oil that can improve the storage stability of the heterogeneous combined materials (isocyanate reactive components) caused by the incompatibility of polyols.

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

[0006] In order to solve the deficiencies in the prior art, the present invention provides a polyether-modified silicone oil with higher controllability and better chemical stability and a preparation method thereof, which has the functions of a foam stabilizer and a polyol compatibilizer. The present invention prepares common polyether and alkyl polyether-modified silicone oils through structural design, and the silicone oil improves the compatibility of the immiscible polyol composition by combining the hydrophilic segment and the hydrophobic segment in the structure, and increases the storage stability of the isocyanate-reactive composite material; at the same time, the Marangoni-Gibbs effect can be effectively generated during the formation of polyurethane foam, so that the bubbles have "instantaneous" stability and continuous stability, and thus a polyurethane foam with stable production, good surface state and fine pores can be obtained.

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

[0008] In order to achieve the above invention object, the technical solution of the present invention is as follows:

[0009] A polyether-modified silicone oil, characterized in that the silicone oil structure contains the following segments at the same time:

[0010] (a) polyoxyethylene ether segment;

[0011] (b) alkylated polyoxyethylene polyoxypropylene ether chain segment, EO and PO can be random copolymers or block copolymers;

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

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

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

[0015]

[0016] wherein the repeating unit a is 1 to 25, b is 2 to 25, and b ≥ a;

[0017] (II) an allyl polyoxyethylene ether component, wherein the allyl polyoxyethylene ether has a structure of:

[0018]

[0019] wherein the repeating unit c is 3 to 50;

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

[0021]

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

[0023] (IV) an alkyl end-capping agent component;

[0024] (V) a catalyst component, the catalyst component comprising a catalyst 1 capable of catalyzing the reaction between the terminal hydroxyl groups of the polyether and the alkyl end-capping agent, and a catalyst 2 capable of catalyzing the reaction between double bonds and silicon-hydrogen bonds.

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

[0026] The catalyst 1 is an alkaline catalyst, preferably, the catalyst is a hydroxide, 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 comprises 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 capping agent to generate alkyl-capped allyl polyoxyethylene polyoxypropylene ether.

[0030] 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.

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

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

[0033] 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 1:1-1.5, preferably 1:1.1-1.2.

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

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

[0036] All reactions were carried out under nitrogen atmosphere.

[0037] In some specific embodiments, the step 1) uses a solid catalyst system. More specifically, the solid catalytic reaction system refers to adding allyl polyoxyethylene polyoxypropylene ether, a solid catalyst, and a water remover into a four-necked flask, replacing 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 halogenated alkane is added dropwise. After the addition is completed, the crude product is obtained by continuing the reaction at 25°C or 50°C for 4-8 hours. Distilled water and phosphoric acid are added to the crude product for water washing and neutralization, stirring at 80-90°C for 1 hour, and then maintaining 70-90°C to allow the reactants to separate, remove the aqueous phase, vacuum dehydrate, and filter the liquid to obtain the end-capped polyether product.

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

[0039] In some specific embodiments, the water scavenger is preferably calcium oxide.

[0040] In some specific embodiments, the step 1) adopts an aqueous solution catalytic system. More specifically, the aqueous solution catalytic reaction system refers to adding a quantitative amount of allyl polyoxyethylene polyoxypropylene ether, a 50-80wt.% hydroxide aqueous solution, and an antioxidant into a four-necked flask. Fully replace with nitrogen under stirring, remove water under reduced pressure, and heat to 110°C to 130°C. After dehydration, react for a period of time, cool to 50°C and drop a quantitative amount of halogenated n-butane, and continue to react for 4-8 hours after the dropwise addition to obtain a crude product. Add distilled water and phosphoric acid to the crude product for water washing and neutralization, stir at 80-90°C for 1h, then maintain 70-90°C to allow the reactants to separate, remove the aqueous phase, vacuum dehydrate, and filter the liquid to obtain the end-capped polyether product.

[0041] The weight of the antioxidant is 2% to 5% of the weight 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 a polyurethane foam composition.

[0044] A polyurethane foam composition is obtained by reacting an isocyanate reactive component A and an isocyanate component B, wherein the isocyanate reactive component A includes but is not limited to a polyol, a catalyst, a blowing agent, a polyether-modified silicone oil, and optionally a chain extender and a flame retardant. The polyether-modified silicone oil is prepared by the aforementioned method or the aforementioned polyether-modified silicone oil.

[0045] The polyether-modified silicone oil of the present invention is particularly preferably used in a white stock containing a combination of polyols of different structures and polarities, because these polyols generally have a tendency to phase 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 the functionality of the polyether polyol A1 is 2 to 5, preferably 3 to 5, the hydroxyl value is 250 to 800 mgKOH / g, and the EO content in the molecular structure is 40 to 100 wt.%; the functionality of the polyol A2 is 2 to 8, the hydroxyl value is 20 to 600 mgKOH / g, and the EO content in the molecular structure is 0 to 20 wt.%.

[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, used in an amount of 25 to 90%, preferably 35 to 80%, more preferably 40 to 75%;

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

[0050] Catalyst A3, dosage 0.01~1%, preferably 0.01~0.1%;

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

[0052] Polyether modified silicone oil, the amount is 0.5-10%, preferably 1-5%;

[0053] Flame retardant A5, the amount is 0-50%, preferably 5-30%, more preferably 10-20%;

[0054] Chain extender A6, the usage amount is 0-30%, preferably 5-15%, more preferably 8-10%.

[0055] More specifically, the polyether polyol A1 mainly uses water and / or polyol as initiators and EO and / or PO as polymerization monomers, and undergoes a chemical reaction under the action of a catalyst to obtain a class of compounds, wherein EO accounts for 40 to 100 wt.%, preferably 50 to 100 wt.%, in the molecular structure, and the polymerization structure of EO and PO can be a block or random structure. 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, neopentyl glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A, bisphenol S, or a mixture thereof, preferably a difunctional small molecule alcohol containing active hydrogen such as propylene glycol or dipropylene glycol, or a trifunctional small molecule alcohol containing active hydrogen such as glycerol or trimethylolpropane; the catalyst includes but is not limited to an alkaline hydroxide, an alkaline alcohol salt, antimony pentachloride, or a mixture thereof.

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

[0057] The catalyst A3 includes but is not limited to heat-sensitive or temperature-sensitive, delayed-type catalysts. Further preferably, the A3 catalyst includes but is not limited to triethylenediamine, pentamethyldialkylenetriamine, tetramethyldialkylenediamine, bis(dimethylaminoethyl)ether, cyclohexylmethyl tertiary amine, stannous octoate, stannous oleate, tin laurate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dithiolate, bismuth octoate, bismuth neodecanoate, bismuth cycloalkaneate, or a combination thereof.

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

[0059] The flame retardant can make the polyurethane foam material obtained by the reaction 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 flame retardant A5 liquid flame retardant 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, toluene diphenyl phosphate, or a combination thereof.

[0060] The chain extender A6, preferably, the A6 chain extender is a polyhydroxy compound with -OH at the end, with a functionality of 1 to 4, preferably 2 to 3, including but not limited to glycerol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, diethylene glycol, dipropylene glycol, methyl propylene glycol, 1,4-butanediol, 1,3-butanediol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-cyclohexanol, 1,6-hexanediol, diethanolamine, triethanolamine, triisopropanolamine, or a combination thereof. Further preferably, the A5 chain extender is selected from ethylene glycol, propylene glycol, glycerol, trimethylolpropane, or a combination thereof.

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

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

[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), p-phenylene diisocyanate (PPDI), 1,4-cyclohexane diisocyanate (CHDI), xylene diisocyanate (XDI), cyclohexane dimethylene diisocyanate (HXDI), trimethyl-1,6-hexamethylene diisocyanate (TMHDI), tetramethyl meta-xylene diisocyanate (TMHDI), isocyanate (TMXDI), norbornane diisocyanate (NBDI), dimethyl biphenyl diisocyanate (TODI), methyl cyclohexyl diisocyanate (HTDI), tetramethylene diisocyanate, pentamethylene diisocyanate, 2,4,6-trimethyl-1,3-phenylene diisocyanate, 4-chloro-6-methyl-1,3-phenylene diisocyanate, poly (tetrafluoroethylene oxide-co-difluoromethyleneoxy) α, ω-diisocyanate, 1,4-butane diisocyanate, 1,8-octane diisocyanate, 1,3-bis (1-isocyanato-1-methylethyl) benzene, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, naphthalene-1,5-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture of these isomers, p-xylylene diisocyanate, and at least one of the prepolymers and 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), p-phenylene diisocyanate (PPDI), 1,4-cyclohexane diisocyanate (CHDI), xylylene diisocyanate (XDI), The invention relates to an isocyanate comprising at least one of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), cyclohexane dimethylene diisocyanate (HXDI), trimethyl-1,6-hexamethylene diisocyanate (TMHDI), tetramethyl meta-xylylene diisocyanate (TMXDI), norbornane diisocyanate (NBDI), dimethyl biphenyl diisocyanate (TODI), methyl cyclohexyl diisocyanate (HTDI) and prepolymers and modified products of the above isocyanates, and more preferably toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and prepolymers and modified products of the above isocyanates.

[0064] In the present invention, the number of moles of hydrogen atoms of active hydrogen in the isocyanate reactive component A is a, the number of moles of isocyanate groups in the isocyanate component B is b, and the isocyanate index R = b / a = 0.8 to 2. In some embodiments of the method according to the present invention, it is preferably 1 to 1.2. It should be noted that the active hydrogen atoms refer to hydrogen atoms that can react with isocyanate groups.

[0065] Compared with the prior art, the present invention has the following beneficial effects:

[0066] The present invention provides a polyether-modified silicone oil and a polyurethane foam composition containing the same. The polyether-modified silicone oil has the functions of a foam stabilizer and a polyol compatibilizer, and can not only improve the long-term storage stability of an isocyanate-reactive composite material, but also obtain a polyurethane foam with stable production and good surface state, thereby achieving a technical effect that cannot be achieved by existing silicone oils.

[0067] The polyether-modified silicone oil is modified by ordinary polyoxyethylene ether and alkyl-terminated polyoxyethylene polyoxypropylene ether to modify the hydrogen-containing silicone oil, wherein the alkylation of polyoxyethylene polyoxypropylene ether gives it better lipophilicity and chemical stability, and improves the quality and effective ingredients of the modified product; and the polyoxyethylene ether contains a more hydrophilic molecular segment. The combination of the hydrophilic segment and the hydrophobic segment in the molecular structure improves the compatibility of the immiscible polyol composition and increases the storage stability of the isocyanate reactive composition in the foam composition. At the same time, the silicone oil of the present invention has a polysiloxane hydrophobic segment, which can effectively reduce the surface tension, and because of its excellent emulsification effect, it can effectively produce the Marangoni-Gibbs effect in the process of forming polyurethane foam, so that the bubbles have "instantaneous" stability and continuous stability, and then a polyurethane foam with stable production and good surface state can be obtained. The obtained polyurethane foam composition has excellent raw material storage stability and foam production stability, reduces production costs and production volatility, and is more suitable for industrialization. DETAILED DESCRIPTION

[0068] The present invention is further described in detail below through specific embodiments, but this should not be construed as limiting the scope of the present invention to the following examples. Various substitutions or changes made according to common technical knowledge and customary means in the art without departing from the above-mentioned method concept of the present invention should be included in the scope of the present invention. In this application, parts and % are usually measured by mass unless otherwise specified.

[0069] Main raw material sources

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

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

[0072] Allyl polyoxyethylene ether APEG-580, molecular weight 580, Wuhan Pushida Biotechnology Co., Ltd.

[0073] Allyl polyoxyethylene ether APEG-800, molecular weight 800, Wuhan Pushida Biotechnology Co., Ltd.

[0074] Allyl polyoxyethylene ether APEG-1100, molecular weight 1100, Wuhan Pushida Biotechnology Co., Ltd.

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

[0076] Hydrogenated 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] Ethyl bromide: 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, from Sinopharm Chemical Reagent Co., Ltd.

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

[0084] Polyether polyol 1-2, glycerol-initiated, EO and PO copolymerized, hydroxyl value 400 mgKOH / g, EO content 40 wt.%, 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 mgKOH / g, EO content 0 wt.%, Dexin Federal Chemical Industry Co., Ltd.;

[0087] Polyol 2-3, polyether polyol, glycerol-initiated, EO and PO copolymerized, hydroxyl value 168 mgKOH / g, EO content 20 wt.%, 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 in Example 1.

[0093] Polyether modified silicone oil 2, prepared as in Example 1.

[0094] Polyether modified silicone oil 3, prepared as in Example 1.

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

[0096] Silicone oil 5: polyether modified silicone oil, with EO / PO mass ratio of 35 / 65, Meside.

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

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

[0099] Main test methods

[0100] Method for testing the storage stability of component A of the polyurethane foam composition: Component A is mixed evenly according to the amount of each component, and then 40g of the raw material is placed in a 60mL transparent sample bottle (diameter 27.5mm, height 140mm), and stored in a 25 / 40℃ constant temperature box. The stability is visually inspected at the following intervals: 2h, 4h, 8h, 16h, 24h, 36h, 48h, and then measured every 24h, with the longest storage test being 720h; if component A shows a phase separation of 1mL in the sample bottle, it is judged as storage stratification.

[0101] Method for testing the foaming stability and production stability of polyurethane foam composition:

[0102] (1) Manual free foaming: According to the types and amounts of each component in Table 1, component A was pre-mixed uniformly according to the amounts of each component, and then components A and B, both of which were at a material temperature of 25° C., were uniformly mixed. 80 g was taken and poured into a 500 mL paper cup. The foaming stability characterization method was as follows: whether there was a tendency of foam collapse during the foaming process, and the surface state of the foam after aging and the pore size of the pores were recorded.

[0103] (2) High-pressure free foam: The high-pressure machine described in Table 3 is used to mix the AB materials. Before loading, the A component is pre-mixed uniformly according to the amount of each component, and then loaded into the high-pressure machine tank. The A tank is opened for stirring, and after internal circulation (A and B materials circulate in their respective tanks and pipelines) for 1 hour, 80g of AB mixture is discharged in a 500mL paper cup. The foaming stability characterization method is: observe whether there is a tendency of foam collapse during the foaming process, and record the pore size of the foam after ripening. The injection pressure is 100 bar, the mixing flow rate is 150 g / s, and the material temperature is 25°C. The production stability characterization method is: after the A component is pre-mixed and loaded, compare whether there is a tendency of foam collapse during the foaming process when the AB mixture is discharged after 1h and 72h of internal circulation in the high-pressure machine, and record the surface state of the foam after ripening and the pore size of the foam.

[0104] Examples and Comparative Examples

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

[0106] Preparation of polyether modified silicone oil 1:

[0107] 1) Preparation of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 1: Add 100g allyl polyoxyethylene polyoxypropylene ether 1 and 18g t-BuONa into a 250mL four-necked flask, replace with nitrogen for several minutes under stirring, and react at 25°C for 2h. Then, at 25°C, add 24g iodomethane dropwise, and continue to react for 4h after the addition is completed to obtain a crude product. Add appropriate distilled water and phosphoric acid to the crude product for water washing and neutralization, adjust pH=6, stir at 80-90°C for 1h, then maintain 70-90°C to allow the reactants to separate, remove the water phase, vacuum dehydrate, and filter the liquid to obtain the capped polyether product.

[0108] 2) Preparation of polyether-modified silicone oil 1: 20 g of hydrogenated silicone oil 1, 85 g of APEG-1100, and 83 g of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 1 were added to a 500 mL three-necked flask, and 0.05 wt% of catalyst chloroplatinic acid was added at the same time, and the mixture was reacted at 100° C. for 8 h under nitrogen protection. After the reaction was completed, the product was rotary evaporated to remove a small amount of low-boiling substances, and polyether-modified silicone oil 1 was obtained.

[0109] Preparation of polyether modified silicone oil 2:

[0110] 1) Preparation of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 2: Add 100g of allyl polyoxyethylene polyoxypropylene ether 1, 10g of 80wt.% KOH aqueous solution, and 2g of anhydrous sodium sulfite as an antioxidant into a four-necked flask. Fully replace with nitrogen under stirring, remove water under reduced pressure, and heat to 130°C. After dehydration, react for 1h, cool to 50°C and drop 12.5g of ethyl bromide. After the addition is completed, continue to react for 4.5h to obtain a crude product. Add appropriate distilled water and phosphoric acid to the crude product for water washing and neutralization, adjust pH=6, stir at 80-90°C for 1h, then maintain 70-90°C to allow the reactants to separate, remove the aqueous phase, vacuum dehydrate, and filter the liquid to obtain the capped polyether product.

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

[0112] Preparation of polyether modified silicone oil 3:

[0113] 1) Preparation of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 3: Add 200g of allyl polyoxyethylene polyoxypropylene ether 2, 13g of KOH, and 200g of water absorbent calcium oxide to a 1000mL four-necked flask, replace with nitrogen for several minutes under stirring, and react at 105°C for 1h. Then cool to 50°C, add 35.4g of ethyl bromide dropwise, and continue to react for 7.5h after the addition to obtain a crude product. Add appropriate distilled water and phosphoric acid to the crude product for water washing and neutralization, adjust pH=6, stir at 80-90°C for 1h, then maintain 70-90°C to allow the reactants to separate, remove the water phase, vacuum dehydrate, and filter the liquid to obtain the capped polyether product.

[0114] 2) Preparation of polyether-modified silicone oil 3: 10 g of hydrogen-containing silicone oil 2, 15 g of APEG-580, and 160 g of alkyl-terminated allyl polyoxyethylene polyoxypropylene ether 3 were added to a 500 mL three-necked flask, and 0.1 wt% of catalyst chloroplatinic acid was added at the same time, and the mixture was reacted at 100° C. for 8 h under nitrogen protection. After the reaction was completed, the product was rotary evaporated to remove a small amount of low-boiling substances, and polyether-modified silicone oil 3 was obtained.

[0115] The amounts of the components in the polyurethane foam compositions in the examples and comparative examples are listed in Table 1. Polyol, KC152, water, tris(2-chloropropyl)phosphate, DEG, and silicone oil are mixed evenly according to the proportions in the following table to obtain component A. The mixing mass ratio of components A and B is calculated according to the isocyanate index, and then the two are mixed evenly to react and foam to obtain polyurethane foam.

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

[0117]

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

[0119]

[0120] Table 3 Specific parameters of high pressure equipment

[0121]

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

[0123]

[0124]

[0125]

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

[0127] It is easy to understand that the above embodiments are only examples for clear explanation and do not mean that the present invention is limited thereto. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims

1. A polyether-modified silicone oil, characterized in that: The silicone oil structure also contains the following segments: (a) polyoxyethylene ether segment; (b) Alkylated polyoxyethylene polyoxypropylene ether chain segments, EO and PO are random copolymers or block copolymers; wherein the molar ratio of the polyoxyethylene ether chain segments to the alkylated polyoxyethylene polyoxypropylene ether chain segments is 1:0.6-4, preferably 1:1-2.

2. The polyether-modified silicone oil according to claim 1, characterized in that Prepared by reacting the following components: (I) an allyl polyoxyethylene polyoxypropylene ether component, wherein the allyl polyoxyethylene polyoxypropylene ether structure is: wherein the repeating unit a is 1 to 25, b is 2 to 25, and b ≥ a; (II) an allyl polyoxyethylene ether component, wherein the allyl polyoxyethylene ether has a structure of: wherein the repeating unit c is 3 to 50; (III) a hydrogen-containing silicone oil component, wherein the hydrogen-containing silicone oil has a structure of: wherein the repeating units m and n are 5 to 15; (IV) an alkyl end-capping agent component; (V) a catalyst component, the catalyst component comprising a catalyst 1 capable of catalyzing the reaction between the terminal hydroxyl groups of the polyether and the alkyl end-capping agent, and a catalyst 2 capable of catalyzing the reaction between double bonds and silicon-hydrogen bonds.

3. The polyether-modified silicone oil according to any one of claims 1 to 2, characterized in that The alkyl end-capping agent component is a halogenated alkane with a structure of RX, wherein R is a C1-4 alkyl group, preferably a methyl group or a n-butyl group; and X is a halogen atom, preferably a Cl or Br atom.

4. The polyether-modified silicone oil according to any one of claims 1 to 3, characterized in that The catalyst 1 is an alkaline catalyst, preferably, the catalyst 1 is a hydroxide; the catalyst 2 is a platinum catalyst, a rhodium catalyst or a palladium catalyst, preferably chloroplatinic acid.

5. A method for preparing the polyether-modified silicone oil according to any one of claims 1 to 4, comprising the following steps: 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 blocking agent to generate alkyl-blocked allyl polyoxyethylene polyoxypropylene ether; 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.

6. The preparation method according to claim 5, characterized in that: The molar ratio of the allyl polyoxyethylene polyoxypropylene ether to the 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 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 1:1-1.5, preferably 1:1.1-1.2; and / or, The catalyst 2 is added in an amount of 0.001% to 0.2 wt.%, based on the total weight of the hydrogen-containing silicone oil, allyl polyoxyethylene ether, and alkyl-terminated allyl polyoxyethylene polyoxypropylene ether being 100 wt.%.

7. The preparation method according to claim 5 or 6, characterized in that: The activation reaction temperature in step 1) is 20-135°C, and the activation time is 1-2h; and / or, the alkylation reaction temperature is 20-60°C, and the alkylation time is 4-8h; and / or, the reaction temperature in step 2) is 100-120°C, and the reaction time is 4-10h.

8. The preparation method according to any one of claims 5 to 7, characterized in that All reactions were carried out under nitrogen atmosphere.

9. A polyurethane foam composition, characterized in that: Obtained by reacting an isocyanate reactive component A and an isocyanate component B, wherein the isocyanate reactive component A comprises a polyol, a catalyst, a blowing 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 to 4, or the polyether-modified silicone oil prepared according to the method according to any one of claims 5 to 8.

10. The polyurethane foam composition according to claim 9, characterized in that The polyol in the isocyanate reactive component A includes at least two incompatible polyether polyols A1 and A2; wherein the functionality of the polyether polyol A1 is 2 to 5, preferably 3 to 5, the hydroxyl value is 250 to 800 mgKOH / g, and the EO content in the molecular structure is 40 to 100 wt.%; the functionality of the polyol A2 is 2 to 8, the hydroxyl value is 20 to 600 mgKOH / g, and the EO content in the molecular structure is 0 to 20 wt.%.

11. The polyurethane foam composition according to claim 10, characterized in that Based on the total mass of the isocyanate-reactive component A, it comprises: Polyether polyol A1, used in an amount of 25 to 90%, preferably 35 to 80%, more preferably 40 to 75%; Polyol A2, in an amount of 5 to 45%, preferably 15 to 35%, more preferably 20 to 30%; Catalyst, dosage 0.01~1%, preferably 0.01~0.1%; Polyether modified silicone oil, the amount is 0.5-10%, preferably 1-5%; Foaming agent, used in an amount of 0.1-2%, preferably 0.5-1%; Flame retardant, the amount is 0-50%, preferably 5-30%, more preferably 10-20%; The chain extender is used in an amount of 0 to 30%, preferably 5 to 15%, and more preferably 8 to 10%.

12. The polyurethane foam composition according to any one of claims 9 to 11, characterized in that The isocyanate component B has an NCO content of 20 to 50 wt.%, a viscosity of 1 to 5000 mPa·s at 25° C.; preferably, the isocyanate index R=0.8 to 2, more preferably 1 to 1.2.

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