Raw material composition for producing polyurethane resin, polyurethane resin, method for producing the same, and product

Abstract

The application relates to a raw material composition for preparing a polyurethane resin, a polyurethane resin and a preparation method and an article thereof, and belongs to the technical field of polyurethane. The raw material composition comprises the following raw materials: an isocyanate-terminated polyurethane prepolymer, a compound containing an isocyanate-reactive group and an alkyne alcohol surfactant. The raw material composition provided in the application embodiment can be injection molded to obtain a polyurethane resin with low density by selecting appropriate components for compounding. Moreover, the compound containing the isocyanate-reactive group can further cooperate with the alkyne alcohol surfactant, so that the occurrence of closed hole shrinkage of the raw material composition in the injection molding process is reduced, thereby enabling the obtained polyurethane resin to have high resilience. Therefore, the polyurethane composition provided in the application embodiment can enable the injection-molded polyurethane resin to have high resilience and low density.

Description

Technical Field

[0001] This application relates to the field of polyurethane resin technology, and particularly to a raw material composition for preparing polyurethane resin, a polyurethane resin, a method for preparing the same, and articles thereof. Background Technology

[0002] Polyurethane resins are widely used in various fields such as footwear, automotive, and packaging due to their excellent flexibility, resilience, abrasion resistance, and low density. However, some fields have higher requirements for the resilience and density of injection-molded polyurethane resins. Currently, injection-molded polyurethane resins have relatively low resilience and high density, falling far short of the requirements in these fields. Therefore, there is an urgent need to develop a polyurethane resin that combines high resilience and low density to meet the requirements of these fields. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the objectives of this application include providing a raw material composition for preparing polyurethane resin, a polyurethane resin, a method for preparing the same, and articles thereof, in order to improve the technical problems of low resilience and high density in injection-molded polyurethane resin.

[0004] In a first aspect, embodiments of this application provide a raw material composition comprising the following raw materials: an isocyanate-terminated polyurethane prepolymer, a compound containing isocyanate reactive groups, and an alkynyl alcohol surfactant.

[0005] The raw material composition provided in this application embodiment, by selecting suitable raw materials for formulation, allows the composition to be injection molded to obtain a low-density polyurethane resin. Furthermore, compounds containing isocyanate reactive groups can further interact with alkynyl alcohol surfactants, reducing closed-cell shrinkage during injection molding, thereby resulting in a polyurethane resin with high resilience. Therefore, the polyurethane composition provided in this application embodiment enables injection-molded polyurethane resin to have both high resilience and low density.

[0006] In some embodiments of this application, the raw material composition is a multi-component composition, which includes:

[0007] The first component, the raw material of the first component includes the reaction product of isocyanate-terminated polyurethane prepolymer obtained by reacting polyisocyanate and a first polyol;

[0008] The second component comprises compounds containing isocyanate reactive groups and alkynyl alcohol surfactants. The compounds containing isocyanate reactive groups include second polyols.

[0009] In some embodiments of this application, alkynyl alcohol surfactants include alkynyl alcohol-terminated organosilicon surfactants.

[0010] Optionally, the mass content of the alkynyl alcohol surfactant is 0.5% to 3% based on the total mass of the second polyol being 100%.

[0011] In some embodiments of this application, the mass content of isocyanate groups is 10% to 15% based on the total mass of the first component as 100%, and the mass content of isocyanate groups is determined by GB / T 13941.

[0012] In some embodiments of this application, the polyisocyanate includes diisocyanate.

[0013] In some embodiments of this application, the diisocyanate includes one or more of methane diphenyl diisocyanate, toluene diisocyanate, terephthalic diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

[0014] In some embodiments of this application, the first polyol and the second polyol independently include one or more of polyether ester polyols, polyester polyols, polyether polyols, and grafted polyols.

[0015] In some embodiments of this application, at least one of the first polyol and the second polyol includes the polyether ester polyol.

[0016] In some embodiments of this application, the number average molecular weight of the polyether ester polyol is 2000 g / mol to 3000 g / mol.

[0017] In some embodiments of this application, the polyether ester polyol includes the product obtained by reacting polytetrahydrofuran polyol with a C2-C10 diacid.

[0018] In some embodiments of this application, the number average molecular weight of the polytetrahydrofuran polyol is 200 g / mol to 500 g / mol.

[0019] In some embodiments of this application, the number average molecular weight of the polyester polyol is 1000 g / mol to 4000 g / mol.

[0020] In some embodiments of this application, the polyester polyol comprises the product obtained by reacting C2-C8 diols and C2-C10 diacids.

[0021] In some embodiments of this application, the C2-C8 diols include one or more of ethylene glycol, propylene glycol, neopentyl glycol, butanediol, pentylene glycol, hexanediol, heptahydrate, and octanediol.

[0022] In some embodiments of this application, the C2-C10 dicarboxylic acids include one or more of oxalic acid, malonic acid, neopentyl glycol, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid.

[0023] In some embodiments of this application, the number average molecular weight of the polyether polyol is 1000 g / mol to 4000 g / mol.

[0024] In some embodiments of this application, the polyether polyol includes one or more of polyethylene oxide polyol, polypropylene oxide polyol, polyethylene oxide-propane copolyol, and polytetrahydrofuran polyol.

[0025] In some embodiments of this application, the number average molecular weight of the grafted polyol is 1000 g / mol to 5000 g / mol.

[0026] In some embodiments of this application, the grafted polyol includes one or more of styrene-grafted polyester polyol, acrylonitrile-grafted polyester polyol, styrene-grafted polyether polyol, and acrylonitrile-grafted polyether polyol.

[0027] In some embodiments of this application, the raw materials for the second component also include one or more of a chain extender / crosslinker, a first foaming agent, and a catalyst.

[0028] In some embodiments of this application, the chain extender / crosslinker includes chain extender and / or crosslinker.

[0029] In some embodiments of this application, the second component comprises the following raw materials in parts by weight:

[0030] Second polyol, 100 parts by weight;

[0031] Chain extender, 5 parts by weight to 20 parts by weight;

[0032] Crosslinking agent, 0.5 parts by weight to 2 parts by weight;

[0033] Acetyl alcohol surfactant, 0.5 parts by weight to 3 parts by weight;

[0034] In some embodiments of this application, the second component further includes the following raw materials in parts by weight:

[0035] First foaming agent, 0.3 parts by weight to 0.5 parts by weight;

[0036] Catalyst, 1 to 2 parts by weight.

[0037] In some embodiments of this application, the chain extender content is 5% to 20% based on the total mass of the second polyol being 100%.

[0038] Optionally, the crosslinking agent content is 0.5% to 2% based on the total mass of the second polyol (100%).

[0039] In some embodiments of this application, the mass content of the chemical foaming agent is less than or equal to 0.5% based on the total mass of the second component being 100%.

[0040] In some embodiments of this application, the chain extender includes at least two first active groups that react with isocyanate groups.

[0041] In some embodiments of this application, the chain extender includes one or more of ethylene glycol, propylene glycol, neopentyl glycol, butanediol, pentylene glycol, hexanediol, heptahydrate, and octanediol.

[0042] In some embodiments of this application, the crosslinking agent includes more than two second active groups that react with the isocyanate groups.

[0043] In some embodiments of this application, the crosslinking agent includes one or more of glycerol, diethanolamine, and triethanolamine.

[0044] In some embodiments of this application, the first foaming agent includes a chemical foaming agent.

[0045] In some embodiments of this application, the catalyst includes amine catalysts and / or organometallic compounds.

[0046] Secondly, embodiments of this application provide a polyurethane resin, which is prepared by reaction molding using the raw material composition of the first aspect of this application.

[0047] Thirdly, embodiments of this application provide a method for preparing the polyurethane resin of the second aspect of this application, comprising:

[0048] A mixture is prepared by mixing a polyurethane prepolymer with isocyanate-terminated ends, a compound containing isocyanate reactive groups, and an alkynol surfactant.

[0049] In the presence of a second foaming agent, the mixture is foamed and molded to obtain a polyurethane resin.

[0050] In some embodiments of this application, the molar ratio of isocyanate reactive groups to isocyanate groups is 0.95 to 1.05.

[0051] In some embodiments of this application, the molar ratio of isocyanate reactive groups to isocyanate groups is 1 to 1.05.

[0052] In some embodiments of this application, the second foaming agent includes a supercritical foaming agent.

[0053] In some embodiments of this application, the supercritical foaming agent includes one or more of supercritical carbon dioxide, supercritical nitrogen, supercritical argon, supercritical ethane, supercritical propane, supercritical butane, supercritical ethylene, and supercritical nitrous oxide.

[0054] In some embodiments of this application, the density of the polyurethane resin is 0.15 g / cm³. 3 ~0.25g / cm 3 .

[0055] In some embodiments of this application, the resilience of the polyurethane resin is greater than or equal to 50%.

[0056] In some embodiments of this application, the resilience of the polyurethane resin is 50% to 60%.

[0057] Fourthly, embodiments of this application also provide an article made of polyurethane resin obtained by foaming and molding the raw material composition of the first aspect of this application and / or polyurethane resin obtained by the second aspect of this application and / or polyurethane resin prepared by the preparation method of the third aspect of this application.

[0058] In some embodiments of this application, the article includes shoe material. Detailed Implementation

[0059] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60–120 and 80–110 are listed for a specific parameter, it is understood that ranges of 60–110 and 80–120 are also expected. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1–3, 1–4, 1–5, 2–3, 2–4, and 2–5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0" and "5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0060] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0061] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0062] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0063] In this document, the expressions "comprising," or similar synonyms such as "including," "containing," and "having," are open-ended and do not exclude additional unlisted elements, steps, or components. The expression "consisting of..." excludes any unspecified elements, steps, or components. The expression "substantially consisting of..." limits the scope to the specified elements, steps, or components, plus optional elements, steps, or components that do not materially affect the essential and novel features of the claimed subject matter. It should be understood that the expression "comprising" encompasses both the expressions "substantially consisting of..." and "consisting of...".

[0064] In this document, the expressions “optional” or “optionally” mean that the event or situation described below may or may not occur, including both the occurrence and non-occurrence of the event or situation.

[0065] In this document, the expression "one or more" or "at least one" can mean 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.

[0066] In this document, the expression "and / or" encompasses both "and" and "or". Elements qualified with "and / or" indicate that either one or any combination thereof is included. For example, A and / or B includes A, B, and A+B. A, B, and / or C includes A, B, C, A+B, A+C, B+C, and A+B+C.

[0067] In a first aspect, embodiments of this application provide a raw material composition for preparing polyurethane resin, the raw material composition comprising the following raw materials: isocyanate-terminated polyurethane prepolymer, a compound containing isocyanate reactive groups, and an alkynyl alcohol surfactant.

[0068] In this article, isocyanate-terminated polyurethane prepolymers refer to polyurethane prepolymers with terminal isocyanate groups.

[0069] A compound containing an isocyanate reactive group is a compound that contains a group that can react with an isocyanate group. For example, the isocyanate reactive group may include hydroxyl, thiol, and amino groups.

[0070] The raw material composition provided in this application embodiment, by selecting suitable raw materials for formulation, allows the composition to be injection molded to obtain a low-density polyurethane resin. Furthermore, compounds containing isocyanate reactive groups can further interact with alkynyl alcohol surfactants, reducing closed-cell shrinkage during injection molding, thereby resulting in a polyurethane resin with high resilience. Therefore, the polyurethane composition provided in this application embodiment enables injection-molded polyurethane resin to have both high resilience and low density.

[0071] In this article, the raw material composition is a combination of raw materials used to synthesize polyurethane resin. The components of the composition can be stored independently or partially mixed before the reaction. After the components are mixed, a polymerization reaction can be carried out to prepare polyurethane resin.

[0072] In some embodiments, the raw material composition is a multi-component composition comprising a first component and a second component. The raw material for the first component comprises a reaction product of an isocyanate-terminated polyurethane prepolymer obtained by reacting a polyisocyanate and a first polyol. The raw material for the second component comprises a compound containing isocyanate reactive groups and an alkynyl alcohol surfactant, wherein the compound containing isocyanate reactive groups comprises a second polyol.

[0073] In the above embodiments, the first and second components can be packaged, stored, and transported independently of each other before the polymerization reaction, which can reduce the manufacturing cost of polyurethane resin.

[0074] In this document, polyisocyanate refers to any compound containing two or more isocyanate (NCO) groups. Polyisocyanates can include monomeric diisocyanates, polymeric isocyanates, isocyanate prepolymers, or mixtures thereof. Polyisocyanates can be aromatic, aliphatic, arylita-, or alicyclic polyisocyanates, or mixtures thereof.

[0075] Polyols are compounds containing two or more hydroxyl groups. When a polyol contains two hydroxyl groups, it is a "diol"; when it contains three hydroxyl groups, it is a "triol"; when it contains exactly four hydroxyl groups, it is a "tetraol"; when it contains five hydroxyl groups, it is a "pentanol", and so on.

[0076] Isocyanate-capped refers to a prepolymer containing at least one free NCO group at one end.

[0077] In some embodiments, alkynyl alcohol surfactants include alkynyl alcohol-terminated silicone surfactants.

[0078] In the above embodiments, the alkynyl alcohol-terminated silicone surfactant can synergistically reduce the density of polyurethane resin with other components, and can further cooperate with polyols and foaming agents to facilitate the formation of a closed-cell, non-shrink structure in polyurethane resin, thereby further improving the resilience and mechanical properties of polyurethane resin.

[0079] In some embodiments, the number-average molecular weight of the alkynyl alcohol-terminated organosilicon surfactant is 4000 g / mol to 10000 g / mol.

[0080] As an example, the above-mentioned organosilicon surfactants may include alkynyl alcohol-modified siloxanes, the structural formula of which is shown below:

[0081]

[0082] Among them, R 1 It is hydrogen, alkyl, or aryl; R 2 It is one or more of hydrogen and alkyl groups; R 3 It is one or more of hydrogen, alkyl, and acyl groups; R 4 It is one or more of hydrogen, alkyl, and aryl, R 5 It is alkyl or aryl; 0≤a≤10; 0≤m≤50; 0≤n≤30.

[0083] In other examples, the structural formula of alkynyl alcohol-modified siloxanes can also be as follows:

[0084]

[0085] Among them, R 4 and R 5 Each independently includes any one of methyl, hydroxy or hydroxymethyl, 1≤m≤50, 0≤n≤50, 0≤x≤30, 0≤y≤30, 0≤o≤30, 0≤p≤30.

[0086] In the above embodiments, the polyether-modified siloxane can be purchased from Zhejiang Runhe Organosilicon New Materials Co., Ltd., for example, grade RH-T1262-2; or from Wuhan Aoke Special Chemical Co., Ltd., for example, grade JC-7000.

[0087] In some embodiments, the mass content of the alkynyl alcohol surfactant is 0.5% to 3% based on the total mass of the second component being 100%.

[0088] For example, the mass content of alkynol surfactants may be, but is not limited to, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, or any combination of two of the above values.

[0089] In some embodiments of this application, the mass content of isocyanate groups is 10% to 15% based on the total mass of the first component as 100%, and the mass content of isocyanate groups is determined by GB / T12009.4-2016.

[0090] In the above embodiments, the mass content of isocyanate groups within the aforementioned range can improve the degree of microphase separation of the polyurethane resin, thereby further improving the mechanical properties and resilience of the polyurethane resin. Furthermore, the mass content of isocyanate groups within the aforementioned range allows for a slower reaction with the foaming agent, thus maintaining a longer open operating time, extending the bubble removal time, and reducing peeling problems caused by density reduction.

[0091] For example, the mass content of isocyanate groups may be, but is not limited to, 10%, 11%, 12%, 13%, 14%, 15%, or any combination of two of the above values.

[0092] In some embodiments, the polyisocyanate includes a diisocyanate.

[0093] In some embodiments, the diisocyanate includes one or more of methane diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), terephthalic diisocyanate (PPDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI).

[0094] In some embodiments, the first polyol and the second polyol independently include one or more of polyether ester polyols, polyester polyols, polyether polyols, and grafted polyols.

[0095] For example, the first polyol includes a polyether ester polyol, while the second polyol does not include a polyether ester polyol; or, the first polyol A does not include a polyether ester polyol, while the second polyol includes a polyether ester polyol; or, the first polyol includes a polyether ester polyol, and the second polyol also includes a polyether ester polyol.

[0096] In some embodiments, the first polyol and the second polyol each independently comprise a polyether ester polyol.

[0097] In the above embodiments, polyether ester polyols can help reduce the density of polyurethane resin while also helping to give the polyurethane resin better mechanical properties.

[0098] In some embodiments, the number-average molecular weight of the polyether ester polyol is 2000 g / mol to 3000 g / mol.

[0099] In this paper, number-average molecular weight has a meaning known in the art and can be measured using instruments and methods well known in the art, such as high-temperature gel permeation chromatography (referred to as high-temperature GPC).

[0100] For example, the number average molecular weight of polyether ester polyols may be, but is not limited to, 2000 g / mol, 2100 g / mol, 2200 g / mol, 2300 g / mol, 2400 g / mol, 2500 g / mol, 2600 g / mol, 2700 g / mol, 2800 g / mol, 2900 g / mol, 3000 g / mol, or any combination of two of the above values.

[0101] In some embodiments, the polyether ester polyol includes the product obtained by reacting polytetrahydrofuran polyol with adipic acid.

[0102] In some embodiments, the number-average molecular weight of the polytetrahydrofuran polyol is 200 g / mol to 500 g / mol.

[0103] In some embodiments, the number-average molecular weight of the polyester polyol is 1000 g / mol to 4000 g / mol.

[0104] For example, the number average molecular weight of the polyester polyol may be, but is not limited to, 1000 g / mol, 1100 g / mol, 1200 g / mol, 1300 g / mol, 1400 g / mol, 1500 g / mol, 1600 g / mol, 1700 g / mol, 1800 g / mol, 1900 g / mol, 2000 g / mol, 2100 g / mol, 2200 g / mol, 2300 g / mol, 2400 g / mol, 2 The range of values ​​is 500 g / mol, 2600 g / mol, 2700 g / mol, 2800 g / mol, 2900 g / mol, 3000 g / mol, 3100 g / mol, 3200 g / mol, 3300 g / mol, 3400 g / mol, 3500 g / mol, 3600 g / mol, 3700 g / mol, 3800 g / mol, 3900 g / mol, 4000 g / mol, or any two of the above values.

[0105] In some embodiments, the polyester polyol comprises a C2-C8 diol and a C2-C10 diacid reacting to obtain the product.

[0106] In some embodiments, the C2-C8 diols include one or more of ethylene glycol, propylene glycol, neopentyl glycol (2,2-dimethyl-1,3-propanediol, abbreviated as NPG), butanediol, pentanediol (1,5-pentanediol), hexanediol, heptahydrate, and octanediol.

[0107] In some embodiments, the C2-C10 dicarboxylic acids include one or more of oxalic acid, malonic acid, neopentyl glycol, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid.

[0108] In some embodiments, the number-average molecular weight of the polyether polyol is 1000 g / mol to 4000 g / mol.

[0109] For example, the number average molecular weight of the polyether polyol may be, but is not limited to, 1000 g / mol, 1100 g / mol, 1200 g / mol, 1300 g / mol, 1400 g / mol, 1500 g / mol, 1600 g / mol, 1700 g / mol, 1800 g / mol, 1900 g / mol, 2000 g / mol, 2100 g / mol, 2200 g / mol, 2300 g / mol, 2400 g / mol, 2 The range of values ​​is 500 g / mol, 2600 g / mol, 2700 g / mol, 2800 g / mol, 2900 g / mol, 3000 g / mol, 3100 g / mol, 3200 g / mol, 3300 g / mol, 3400 g / mol, 3500 g / mol, 3600 g / mol, 3700 g / mol, 3800 g / mol, 3900 g / mol, 4000 g / mol, or any two of the above values.

[0110] In some embodiments, the polyether polyol includes one or more of polyethylene oxide polyol, polypropylene oxide polyol, polyethylene oxide-propane copolyol, and polytetrahydrofuran polyol.

[0111] In some embodiments, the number-average molecular weight of the grafted polyol is 1000 g / mol to 5000 g / mol.

[0112] For example, the number-average molecular weight of the grafted polyol may be, but is not limited to, 1000 g / mol, 1100 g / mol, 1200 g / mol, 1300 g / mol, 1400 g / mol, 1500 g / mol, 1600 g / mol, 1700 g / mol, 1800 g / mol, 1900 g / mol, 2000 g / mol, 2100 g / mol, 2200 g / mol, 2300 g / mol, 2400 g / mol, 2500 g / mol, 2600 g / mol, 2700 g / mol, 2800 g / mol, 2900 g / mol, 3 The range of values ​​is 000 g / mol, 3100 g / mol, 3200 g / mol, 3300 g / mol, 3400 g / mol, 3500 g / mol, 3600 g / mol, 3700 g / mol, 3800 g / mol, 3900 g / mol, 4000 g / mol, 4100 g / mol, 4200 g / mol, 4300 g / mol, 4400 g / mol, 4500 g / mol, 4600 g / mol, 4700 g / mol, 4800 g / mol, 4900 g / mol, 5000 g / mol, or any two of the above values.

[0113] In some embodiments, the grafted polyol includes one or more of styrene-grafted polyester polyol, acrylonitrile-grafted polyester polyol, styrene-grafted polyether polyol, and acrylonitrile-grafted polyether polyol.

[0114] In the embodiments of this application, the raw materials of the second component may further include one or more of the following: chain extender, first foaming agent, and catalyst.

[0115] In some embodiments, the chain extender / crosslinker includes a chain extender and / or a crosslinker.

[0116] In some embodiments, the second component comprises the following raw materials in parts by weight:

[0117] Second polyol, 100 parts by weight;

[0118] Chain extender, 5 parts by weight to 20 parts by weight;

[0119] Crosslinking agent, 0.5 parts by weight to 2 parts by weight;

[0120] Alkyne alcohol surfactant, 0.5 parts by weight to 3 parts by weight.

[0121] In some embodiments, the second component further comprises, by weight, the following raw materials:

[0122] First foaming agent, 0.3 parts by weight to 0.5 parts by weight;

[0123] Catalyst, 1 to 2 parts by weight.

[0124] In some embodiments, the chain extender content is 5% to 20% based on the total mass of the second polyol being 100%.

[0125] In some embodiments, the crosslinking agent content is 0.5% to 2% based on the total mass of the second polyol being 100%.

[0126] In some embodiments, the chain extender includes at least two first active groups that react with isocyanate groups.

[0127] In some embodiments, the chain extender includes one or more of ethylene glycol, propylene glycol, neopentyl glycol, butanediol, pentylene glycol, hexanediol, heptahydrate, and octanediol.

[0128] In some embodiments, the crosslinking agent includes more than two second active groups that react with the isocyanate groups.

[0129] In some embodiments, the crosslinking agent includes one or more of glycerol, diethanolamine, and triethanolamine.

[0130] In some embodiments, the first foaming agent includes a chemical foaming agent.

[0131] In the above embodiments, the addition of chemical foaming agents can improve foaming efficiency.

[0132] In some embodiments, the mass content of the first chemical foaming agent is less than or equal to 0.5% based on the total mass of the second component being 100%.

[0133] In some embodiments, the first chemical foaming agent comprises water.

[0134] In the embodiments of this application, the addition of a catalyst can shorten the reaction time. The amount used can be the conventional amount prepared using known polyurethane. The catalyst can be prepared using known polyurethane.

[0135] In some embodiments, the catalyst includes amine catalysts and / or organometallic compounds.

[0136] For example, amine catalysts may include tertiary amine catalysts, which may include aliphatic and alicyclic tertiary amine catalysts of monoamines, diamines, or triamines. Specifically, tertiary amine catalysts may include one or more of, for example, triethylenediamine, 1,4-diazabicyclo[2.2.2]octane, 6-(dibutylamino)-1,8-diazabicyclo[5.4.0]undec-7-ene, and dimethylcyclohexylamine. Amine catalysts may also include A33 (A33 is a solution formed by dissolving 33% triethylenediamine solid in 67% diethylene glycol).

[0137] Organometallic compounds may include organic catalysts based on tin, bismuth, zinc, aluminum, and zirconium. Specifically, organometallic compounds may include one or more of dibutyltin dilaurate, dibutyltin thiolate, dibutyltin sulfide, dimethyltin thiolate, mercaptodibutyltin ester, zirconium diketoate, aluminum diketoate, bismuth neodecanoate, and zincamine compounds.

[0138] In some specific embodiments, the catalyst can be commercially available Fomrez UL-29, Fomrez32, Fomrez54, etc.

[0139] Secondly, embodiments of this application provide a polyurethane resin, which is prepared by reaction molding using the raw material composition of the first aspect of this application.

[0140] Thirdly, embodiments of this application provide a method for preparing the polyurethane resin of the second aspect of this application, comprising:

[0141] A mixture is prepared by mixing a polyurethane prepolymer with isocyanate-terminated ends, a compound containing isocyanate reactive groups, and an alkynol surfactant.

[0142] In the presence of a second foaming agent, the mixture is foamed and molded to obtain a polyurethane resin.

[0143] In some embodiments, the molar ratio of the isocyanate reactive group to the isocyanate group is 0.95 to 1.05.

[0144] In some embodiments, the molar ratio of isocyanate reactive groups to isocyanate groups is 1 to 1.05.

[0145] For example, the molar ratio of the isocyanate reactive group to the isocyanate group may be, but is not limited to, 0.95, 0.96, 0.97, 0.98, 0.99, 1, 1.01, 1.02, 1.03, 1.04, 1.05 or any combination of two of the above values.

[0146] In some embodiments, the second blowing agent includes a supercritical blowing agent.

[0147] In this paper, supercritical refers to a state where the pressure is above the critical pressure and the temperature is above the critical temperature.

[0148] In some embodiments, the supercritical blowing agent includes one or more of supercritical carbon dioxide, supercritical nitrogen, supercritical argon, supercritical ethane, supercritical propane, supercritical butane, supercritical ethylene, and supercritical nitrous oxide.

[0149] In some embodiments, the density of the polyurethane resin is 0.15 g / cm³. 3 ~0.25g / cm 3 .

[0150] In some embodiments, the resilience of the polyurethane resin is greater than or equal to 50%.

[0151] In some embodiments, the resilience of the polyurethane resin is 50% to 60%.

[0152] Fourthly, embodiments of this application also provide an article of manufacture made from polyurethane resin obtained by injection molding using the raw material composition of the first aspect of this application and / or polyurethane resin obtained by the second aspect of this application and / or polyurethane resin prepared by the preparation method of the third aspect of this application.

[0153] In some embodiments, the above-mentioned articles may be sheets, mats, adhesives, sheaths of threads, protective clothing, automotive parts, shoe components, coatings, foam laminates, automotive shells, awnings, tarpaulins, roofing products, steering wheels, powder coatings, handles, grips, computer components, strips, inlays, conveyor belts, or fabrics.

[0154] Furthermore, the article includes footwear materials, which may include one or more of the following: outsole, midsole, sole, overmolded product, genuine leather product, synthetic leather product, upper, laminated product, coated product, boot, sandal, overshoe, and plastic shoe.

[0155] I. Implementation Examples

[0156] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0157] The features and performance of this application will be further described in detail below with reference to the embodiments.

[0158] Example 1

[0159] This embodiment provides a method for preparing polyurethane resin, including:

[0160] The first component is provided: 100 kg of polyether ester polyol reacts with diisocyanate MDI to obtain a reaction product containing polyurethane prepolymer, wherein the number average molecular weight of the polyether ester polyol is 2000 g / mol, the polyether ester polyol is adipic acid-grafted polytetrahydrofuran ether polyol (PTMEG has a number average molecular weight of 300 g / mol), and the NCO mass content of the first component is 12.5%.

[0161] The second component is provided as follows: 70 kg of polyether ester polyol (the number average molecular weight of the polyether ester polyol is 2000 g / mol, the polyether ester polyol is adipic acid-grafted polytetrahydrofuran polyol, and the number average molecular weight of PTEMG is 300 g / mol), 30 kg of polystyrene-grafted polybutylene adipate polyol, 1.0 kg of crosslinking agent diethanolamine, 5 kg of ethylene glycol, 0.3 kg of water, 1.5 kg of catalyst A33 (A33 is a solution formed by dissolving 33% triethylenediamine solid in 67% dipropylene glycol), 0.3 kg of catalyst Fomorez UL-29, and 2 kg of alkynyl alcohol surfactant. The surfactant is an alkynyl alcohol organosilicon surfactant from Zhejiang Runhe Organosilicon New Materials Co., Ltd., brand name RH-T1262-2.

[0162] The first and second components are mixed and injected into a mold, and supercritical carbon dioxide is introduced for injection molding to obtain polyurethane resin. The molar ratio of the isocyanate reactive groups in the second component to the isocyanate groups in the first component is 1:1.

[0163] Examples 2-23

[0164] The differences between Examples 2-23 and Example 1 are shown in Table 1. Polyurethane resins with basically consistent density can be prepared through Examples 1-23.

[0165] Comparative Examples 1-3

[0166] The differences between Comparative Examples 1 to 3 and Example 1 are shown in Table 1.

[0167] Table 1 lists the differences between the raw material compositions in Examples 1-23 and Comparative Examples 1-3, respectively.

[0168]

[0169]

[0170]

[0171]

[0172] Note: In Table 1, 1 part by weight can be converted to 1 kg;

[0173] Comparative Examples 1-3 show that the amount of the first foaming agent needs to be increased, as a small amount of the first foaming agent will not result in good molding.

[0174] The R value represents the molar ratio of the isocyanate reactive group to the isocyanate group;

[0175] The polyether ester polyols used in Examples 1-23 and Comparative Examples 1-3 were all obtained by polymerizing adipic acid and different types of alcohols.

[0176] II. Testing Section

[0177] The polyurethane resins prepared in the above embodiments and comparative examples can be tested for density, resilience, and mechanical properties according to the test methods described in the following national standards.

[0178] The density test method refers to the method described in GB / T 1033, the resilience test method refers to the method described in GB-T 6670-2008, the hardness test method refers to the method described in GB / T 531.1, the compression set test method refers to the method described in GB / T 7759, the tear strength test method refers to the method described in GB / T 529, and the tensile strength test method refers to the method described in GB / T 528.

[0179] III. Analysis of Test Results for Each Embodiment and Comparative Example

[0180] Polyurethane resins for each embodiment and comparative example were prepared according to the above method, and their properties were measured. The results are shown in Table 2 below.

[0181]

[0182] According to Tables 1 and 2, a comparison of the test results of Examples 1-23 and Comparative Examples 1-3 shows that, since Comparative Examples 1-3 did not add the alkynyl alcohol surfactant of this application, the polyurethane resins prepared using other surfactants had higher densities. In contrast, the examples of this application, through the rational combination of isocyanate-terminated polyurethane prepolymer, compounds containing isocyanate reactive groups, and alkynyl alcohol surfactants, can produce polyurethane resins with low density and high resilience through injection molding.

[0183] The embodiments described above are some, but not all, of the embodiments of this application. The detailed description of the embodiments of this application is not intended to limit the scope of the claimed application, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

Claims

1. A raw material composition for preparing polyurethane resin, characterized in that, The raw material composition includes: Isocyanate-terminated polyurethane prepolymers; Compounds containing isocyanate reactive groups; and Alkyne alcohol surfactants.

2. The raw material composition according to claim 1, characterized in that, The raw material composition is a multi-component composition, which includes: The first component, the raw material of the first component includes the reaction product of the isocyanate-terminated polyurethane prepolymer obtained by reacting polyisocyanate and a first polyol; The second component, the raw materials of which include the compound containing the isocyanate reactive group and the alkynol surfactant, wherein the compound containing the isocyanate reactive group includes a second polyol.

3. The raw material composition according to claim 2, characterized in that, The alkynol surfactants include alkynol-terminated organosilicon surfactants; Optionally, based on the total mass of the second polyol being 100%, the mass content of the alkynyl alcohol surfactant is 0.5% to 3%.

4. The raw material composition according to claim 2 or 3, characterized in that, Based on the total mass of the first component being 100%, the mass content of the isocyanate group is 10% to 15%, and the mass content of the isocyanate group is determined by GB / T 12009.4-2016; Optionally, the polyisocyanate includes a diisocyanate; Optionally, the diisocyanate includes one or more of methane diphenyl diisocyanate, toluene diisocyanate, terephthalic diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate; Optionally, the first polyol and the second polyol each independently comprise one or more of polyether ester polyols, polyester polyols, polyether polyols, and grafted polyols; Optionally, at least one of the first polyol and the second polyol comprises the polyether ester polyol.

5. The raw material composition according to claim 4, characterized in that, The polyether ester polyol has a number average molecular weight of 2000 g / mol to 3000 g / mol; optionally, the polyether ester polyol includes the product obtained by reacting polytetrahydrofuran polyol with a C2 to C10 diacid; optionally, the polytetrahydrofuran polyol has a number average molecular weight of 200 g / mol to 500 g / mol. And / or, the number average molecular weight of the polyester polyol is 1000 g / mol to 4000 g / mol; optionally, the polyester polyol comprises the product obtained by reacting a C2-C8 diol with a C2-C10 diacid; optionally, the C2-C8 diol comprises one or more of ethylene glycol, propylene glycol, neopentyl glycol, butanediol, pentylene glycol, hexanediol, heptahydrate, and octyl glycol; optionally, the C2-C10 diacid comprises one or more of oxalic acid, malonic acid, neopentyl glycol, succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid. And / or, the number average molecular weight of the polyether polyol is 1000 g / mol to 4000 g / mol; optionally, the polyether polyol includes one or more of polyethylene oxide polyol, polyethylene oxide polyol, polyethylene oxide-propane copolyol and polytetrahydrofuran polyol. And / or, the number average molecular weight of the grafted polyol is 1000 g / mol to 5000 g / mol; optionally, the grafted polyol includes one or more of styrene-grafted polyester polyol, acrylonitrile-grafted polyester polyol, styrene-grafted polyether polyol, and acrylonitrile-grafted polyether polyol.

6. The raw material composition according to claim 2, characterized in that, The raw materials for the second component also include one or more of the following: chain extender / crosslinker, first foaming agent, and catalyst; Optionally, the chain extender / crosslinker includes a chain extender and / or a crosslinker; Optionally, the second component comprises the following raw materials in parts by weight: Second polyol, 100 parts by weight; Chain extender, 5 parts by weight to 20 parts by weight; Crosslinking agent, 0.5 parts by weight to 2 parts by weight; Acetyl alcohol surfactant, 0.5 parts by weight to 3 parts by weight; Optionally, based on the weight parts of the second component, it further includes the following raw materials: First foaming agent, 0.3 parts by weight to 0.5 parts by weight; Catalyst, 1 to 2 parts by weight.

7. The raw material composition according to claim 6, characterized in that, The chain extender includes at least two first active groups that react with the isocyanate group; Optionally, the chain extender includes one or more of ethylene glycol, propylene glycol, neopentyl glycol, butanediol, pentylene glycol, hexanediol, heptahydrate, and octanediol; Optionally, the crosslinking agent includes more than two second active groups that react with the isocyanate groups; Optionally, the crosslinking agent includes one or more of glycerol, diethanolamine, and triethanolamine; Optionally, based on the total mass of the second polyol being 100%, the mass content of the chain extender is 5% to 20%; Optionally, based on the total mass of the second polyol being 100%, the mass content of the crosslinking agent is 0.5% to 2%; Optionally, the first foaming agent includes a chemical foaming agent; Optionally, based on the total mass of the second component being 100%, the mass content of the chemical foaming agent is less than or equal to 0.5%. Optionally, the chemical foaming agent includes water; Optionally, the catalyst includes amine catalysts and / or organometallic compounds.

8. A polyurethane resin, characterized in that, The polyurethane resin is prepared by reaction molding using the raw material composition according to any one of claims 1 to 7.

9. A method for preparing the polyurethane resin as described in claim 8, comprising: A mixture is prepared by mixing a polyurethane prepolymer with isocyanate-terminated ends, a compound containing isocyanate reactive groups, and an alkynol surfactant. In the presence of a second foaming agent, the mixture is foamed and molded to obtain the polyurethane resin; Optionally, the molar ratio of the isocyanate reactive group to the isocyanate group is 0.95 to 1.05; Optionally, the molar ratio of the isocyanate reactive group to the isocyanate group is 1 to 1.05; Optionally, the second foaming agent includes a supercritical foaming agent; Optionally, the supercritical foaming agent includes one or more of supercritical carbon dioxide, supercritical nitrogen, supercritical argon, supercritical ethane, supercritical propane, supercritical butane, supercritical ethylene, and supercritical nitrous oxide. Optionally, the density of the polyurethane resin is 0.15 g / cm³. 3 ~0.25g / cm 3 ; Optionally, the resilience of the polyurethane resin is greater than or equal to 50%; Optionally, the resilience of the polyurethane resin is 50% to 60%.

10. An article characterized in that, The article is made of polyurethane resin obtained by foaming and molding the raw material composition according to any one of claims 1 to 7 and / or polyurethane resin obtained by the preparation method according to claim 8 and / or polyurethane resin obtained by the preparation method according to claim 9; Optionally, the article includes shoe materials.

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