Floating body material and preparation method thereof

Abstract

The invention relates to the field of polyurethane materials, in particular to a floating body material which has the advantages of low density and high mechanical strength, and further relates to a preparation method of the floating body material. The polyurethane composition used in the floating body material can form continuous phase foam with high mechanical strength and low density, and the floating body material with low density, high mechanical strength and high durability is obtained after the polyurethane composition is mixed with other foam materials. The floating body material can be directly used as a floating material for aquatic product culture. The floating body material is long in service life and cannot be broken to enter a water area to affect the water area environment in the using process. The floating body material disclosed by the invention can be prepared on site in a recovery place of other foam materials or floating body materials, and the obtained floating body material can be directly put into use, so that the transportation cost, the time cost and the labor cost are saved. The shell of the floating body material can be used as the shell of the floating body material and can also be used as a storage container of the polyurethane composition, and transportation and storage are facilitated.

Description

Technical Field

[0001] The present invention relates to the field of polyurethane, in particular to a floating material having the advantages of low density and high mechanical strength. The present invention also relates to a preparation method of the floating material. Background Art

[0002] Expanded polystyrene (EPS) is a hard and tough closed-cell foam that has a variety of applications related to insulation and packaging. EPS can be recycled to obtain recycled polystyrene. However, the floats made of EPS foam have a short service life due to their weak mechanical properties. In addition, after the use cycle, because it is not easy to degrade by itself in the natural environment, coupled with poor management and people's weak environmental awareness, the phenomenon of discarded floats being discarded at will is quite common, which has an extremely serious negative impact on the marine ecological environment and causes serious environmental problems.

[0003] Existing aquaculture floats also have hollow structures made of high-density polyethylene (HDPE), but the HDPE shell must reach a certain thickness to ensure sufficient mechanical strength, withstand environmental erosion, and withstand daily wear and tear by personnel. At the same time, this will cause a weakening of buoyancy.

[0004] CN103342517A provides a technical method for preparing fluidized concrete using waste EPS as filler. EPS is crushed into granules, mixed with fly ash, silica fume, FDN high-efficiency composite water reducer and other ingredients, and mixed with medium sand and gravel to form fluidized concrete. The product can be used for lightweight construction purposes. Summary of the invention

[0005] On the one hand, the present invention provides a floating material, which includes polyurethane foam, other foam materials different from polyurethane foam, and a shell material wrapping the polyurethane foam, wherein the other foam materials are at least partially wrapped by the polyurethane foam, the mass ratio of the other foam materials to the polyurethane foam material is greater than or equal to 1:9, and the other foam materials include one or more of polyolefin foam materials, polystyrene foam materials, polyester foam materials and any combination thereof; the polyurethane foam is made of a polyurethane composition, and the polyurethane composition includes (A) an isocyanate component, (B) an isocyanate reactive component and (C) an additive, wherein

[0006] (A) an isocyanate component comprising at least one polyisocyanate;

[0007] (B,) an isocyanate-reactive component comprising:

[0008] (b1) at least one polyether polyol based on polyalkylene oxide, having a hydroxyl value of 100 to 500 mgKOH / g and a functionality of 2 to 10,

[0009] Optionally (b2) at least one polyester polyol;

[0010] (C) The additive component comprises one or more of the following:

[0011] (c1) a catalyst;

[0012] (c2) a blowing agent;

[0013] (c3) Foam stabilizer.

[0014] On the other hand, the present invention provides a method for preparing the floating material. DETAILED DESCRIPTION

[0015] General Definitions and Terminology

[0016] Unless otherwise indicated, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety.

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event of a conflict, the definitions provided herein shall prevail.

[0018] Unless otherwise stated, all percentages, parts, ratios, etc. are by weight. It will be appreciated by those skilled in the art that the sum of all components in the composition can be suitably 100%. When providing quantity, concentration or other values ​​or parameters as scope, preferred range or preferred upper limit and lower limit or specific value, it should be understood as specifically disclosing all ranges formed by paired values ​​from any upper limit range or preferred value and any lower limit range or preferred value, and no matter whether scope is disclosed individually. Unless otherwise stated, when numerical range is quoted herein, described scope refers to and includes its endpoints and integers and fractions in all such scopes.

[0019] The terms "about" and "approximately" when used with a numerical variable generally refer to the value of that variable and all values ​​of that variable are within experimental error (e.g., within a 95% confidence interval for the mean) or within ±10% of the specified value, or a wider range.

[0020] The term "optional" or "optionally" as used herein means that the event or situation described subsequently may or may not occur, and the description includes the occurrence of the event or situation and the non-occurrence of the event or situation, and also includes the situation where the content described subsequently is arbitrarily selected. For example, when the content of a certain ingredient in this article is 0%-5%, it means that the component can be optionally present, that is, it covers the situation of absence (0%) and presence (>0-5%).

[0021] The terms "include", "comprising", "having", "containing" or "involving" and other variations thereof herein are inclusive or open-ended and do not exclude other unlisted elements or method steps. It will be understood by those skilled in the art that the above terms such as "comprising" encompass the meaning of "consisting of". The expression "consisting of" excludes any element, step or ingredient not specified. The expression "consisting essentially of" means that the scope is limited to the specified elements, steps or ingredients, plus the optional presence of elements, steps or ingredients that do not substantially affect the basic and new features of the claimed subject matter. It should be understood that the expression "comprising" encompasses the expressions "consisting essentially of" and "consisting of". The term "selected from..." refers to one or more elements in the groups listed later, independently selected, and may include combinations of two or more elements therein.

[0022] As used herein, the terms "one or more" or "at least one" refer to one, two, three, four, five, six, seven, eight, nine or more.

[0023] The term "and / or" as used herein encompasses "and" and "or". A plurality of elements, components or steps defined with "and / or" represent any one of the elements, components or steps and any combination thereof. For example, A and / or B encompasses A, B and A+B; A, B and / or C encompasses A, B, C, A+B, A+C, B+C and A+B+C.

[0024] Unless otherwise specified, the terms "combination thereof", "any combination thereof" and "mixture thereof" mean a multi-component mixture of the elements, such as a mixture of two, three, four and up to the maximum possible multi-component mixture.

[0025] In addition, if the number of parts or components of the present invention is not indicated before, it means that there is no limit to the number of occurrences (or existence) of the parts or components. Therefore, it should be interpreted as including one or at least one, and the singular form of the parts or components also includes the plural form, unless the numerical value obviously represents the singular.

[0026] As used herein, "plurality" means two or more than two, unless otherwise specifically defined. Unless the context clearly indicates, "a" or "an" may include singular references as well as plural references.

[0027] The functionality of a polyol refers to a value determined according to the industry formula: functionality = hydroxyl value x molecular weight / 56100; wherein the molecular weight is determined by GPC high performance liquid chromatography, and the test method can refer to GB / T 21863-2008.

[0028] The hydroxyl value refers to the number of milligrams of potassium hydroxide equivalent to the hydroxyl group in 1g of sample. The test method can refer to ISO14900-2017.

[0029] When used in the present invention, unless otherwise indicated, functionality and hydroxyl value refer to the average functionality and average hydroxyl value.

[0030] In one aspect, the present invention relates to a floating material, which comprises polyurethane foam, other foam materials different from polyurethane foam, and a shell material wrapping the polyurethane foam, wherein the other foam materials are at least partially wrapped by the polyurethane foam, the mass ratio of the other foam materials to the polyurethane foam material is greater than or equal to 1:9, and the other foam materials comprise one or more of polyolefin foam materials, polystyrene foam materials, polyester foam materials, and any combination thereof; the polyurethane foam is made of a polyurethane composition, and the polyurethane composition comprises (A) an isocyanate component, (B) an isocyanate reactive component, and (C) an additive, wherein

[0031] (A) an isocyanate component comprising at least one polyisocyanate;

[0032] (B) an isocyanate-reactive component comprising:

[0033] (b1) at least one polyether polyol based on polyalkylene oxide, having a hydroxyl value of 100 to 500 mgKOH / g and a functionality of 2 to 10,

[0034] Optionally (b2) at least one polyester polyol;

[0035] (C) The additive component comprises one or more of the following:

[0036] (c1) a catalyst;

[0037] (c2) a blowing agent;

[0038] (c3) Foam stabilizer.

[0039] The isocyanate component may comprise at least one polyisocyanate. The polyisocyanate may be one or more of any pure aliphatic, alicyclic and aromatic polyisocyanates known for preparing polyurethanes, preferably aromatic polyisocyanates. The polyisocyanates of the present invention are isocyanates comprising two or more isocyanate groups, and therefore include diisocyanates and triisocyanates.

[0040] Aromatic polyisocyanates include, but are not limited to: toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (pMDI), 1,5-naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), one or more of their polymers and combinations thereof. The aromatic polyisocyanate includes its isomers, for example, diphenylmethane diisocyanate (MDI) includes one or more of 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate and mixtures thereof.

[0041] Pure aliphatic polyisocyanates include, but are not limited to, one or more of hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), polymers thereof, or combinations thereof.

[0042] Alicyclic polyisocyanates include, but are not limited to, methylcyclohexyl diisocyanate (HTDI), 4,4'-dicyclohexylmethane diisocyanate (H 12 MDI), isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate (CHDI), polymers thereof and combinations thereof.

[0043] The functionality of the polyisocyanate used in the present invention is preferably 2.0-3.5, particularly preferably 2.1-2.9. The viscosity of the polyisocyanate is preferably 5-700 mPa·s, particularly preferably 10-300 mPa·s, more particularly preferably 100-300 mPa·s, measured at 25° C. according to DIN 53019-1-3.

[0044] The isocyanate component may include polyisocyanate dimers, trimers, tetramers, pentamers, other polymers or combinations thereof.

[0045] In a preferred embodiment of the present invention, the (A) isocyanate component may be selected from one or more of diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (pMDI), polymers thereof, prepolymers thereof and combinations thereof.

[0046] In a preferred embodiment of the present invention, the (A) isocyanate component comprises 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and / or polyphenylmethane polyisocyanate (pMDI).

[0047] In a more preferred embodiment of the present invention, the (A) isocyanate component comprises 95% or more, more preferably 97% or more of 4,4'-MDI, based on the weight percentage of the (A) isocyanate component.

[0048] In a more preferred embodiment of the present invention, the (A) isocyanate component comprises more than 95%, more preferably more than 97% pMDI, based on the weight percentage of the (A) isocyanate component.

[0049] Polyisocyanates of the present invention can also include liquefied MDI variants, which are modified MDIs known in the art, and which have a higher functionality than MDI. Common liquefied MDI can be a liquid product obtained by introducing urethane, allophanate, urea, biuret, carbodiimide, uretonimine and / or isocyanurate residues (residues) etc. into MDI, and combinations thereof.

[0050] The isocyanate NCO% content in the (A) isocyanate component of the present invention is preferably 5-33.6%, more preferably 10-32%, based on the total weight of the isocyanate component, measured in accordance with GB / T12009.4-2016.

[0051] Isocyanate-terminated prepolymers can also be used as (A) isocyanate component, which can be prepared by reacting an excess of polyisocyanate or a combination thereof with a polyol compound, wherein the molar ratio of isocyanate NCO in the polyisocyanate to hydroxyl OH in the polyol is preferably 2: 1 to 4: 1. Those skilled in the art are familiar with these compounds and their preparation methods.

[0052] The isocyanate-terminated prepolymer is prepared by reacting an excess of polyisocyanate with a polyol to obtain a prepolymer with a specified NCO value, wherein the NCO% content may be 5-20%, measured according to GB / T 12009.4-2016. Wherein, the polyol may be a polyether polyol and / or a polyester polyol. Methods for preparing prepolymers have been described in the art. The relative amounts of polyisocyanate and polyol depend on their equivalents and the desired NCO value, and can be easily determined by a person skilled in the art. The hydroxyl value of the polyether polyol and / or polyester polyol is preferably 28-800 mgKOH / g; the functionality is preferably 2-6. If desired, the preparation reaction of the isocyanate-terminated prepolymer may be carried out in the presence of a catalyst, preferably a catalyst capable of enhancing the formation of urethane groups, such as a tertiary amine catalyst and an organic tin compound. The reaction time may be 30 minutes to 4 hours, and the reaction temperature may be 50 to 90°C.

[0053] In the present invention, the (A) isocyanate component may be composed of one or more polyisocyanates and / or isocyanate-terminated prepolymers.

[0054] The polyurethane foam described in the present invention can be obtained by reacting (A) an isocyanate component with (B) an isocyanate-reactive component, or by first reacting (A) an isocyanate component with (B) an isocyanate-reactive component to obtain an isocyanate prepolymer, and then reacting the isocyanate prepolymer to obtain the polyurethane foam, or by both of the above methods to obtain the polyurethane foam.

[0055] The (B) isocyanate reactive component of the present invention refers to a component that can react with polyisocyanate to form polyurethane, and can be a component containing hydroxyl groups, such as a polyol component. Various additives commonly used or added in the polyurethane foam forming process are generally understood to be included in the (C) additive component.

[0056] In one embodiment, the (B) isocyanate-reactive component may include: (b1) a polyalkylene oxide-based polyether polyol.

[0057] The polyether polyol can be prepared by a known process, for example, by reacting an olefin oxide with an initiator in the presence of a catalyst. The catalyst may include, but is not limited to, one or more of an alkaline hydroxide, an alkaline alkoxide, antimony pentachloride, boron fluoride etherate, and combinations thereof. The olefin oxide includes, but is not limited to, one or more of tetrahydrofuran, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and combinations thereof.

[0058] In one embodiment of the present invention, the oxidized olefin is an alkylene oxide, preferably an alkylene oxide having 2 to 6 carbon atoms, more preferably one or more of ethylene oxide, propylene oxide and tetrahydrofuran, especially propylene oxide.

[0059] The initiator can be adjusted according to the properties of the polyether polyol such as functionality and viscosity, and is preferably but not limited to polyhydroxy compounds and / or polyamines, more preferably polyhydroxy compounds, or a combination of polyhydroxy compounds and polyamines.

[0060] The polyol may include one or more of sorbitol, sucrose, 1,3-propylene glycol, glycerol, ethylene glycol, 1,2-propylene glycol, diethylene glycol, trimethylolpropane, bisphenol A, bisphenol S and combinations thereof, preferably one or more of sucrose, propylene glycol, sorbitol, glycerol and combinations thereof.

[0061] The polyamine may include one or more of ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, toluenediamine, meta-phenylenediamine and combinations thereof, preferably meta-phenylenediamine and / or ethylenediamine.

[0062] In one embodiment of the present invention, the initiator comprises a polyhydroxy compound and a polyamine.

[0063] In a more preferred embodiment of the present invention, the initiator comprises a polyhydroxy compound and a polyamine, wherein the polyhydroxy compound is selected from one or more of sucrose, propylene glycol, sorbitol, glycerol and a combination thereof, and the polyamine is selected from m-phenylenediamine and / or ethylenediamine.

[0064] The polyether polyols described certainly also include embodiments of two or more different polyether polyols. This is also the case within the polyol class. Thus, if, for example, "polyether polyol" (or "polyester polyol", etc.) is mentioned below, the term certainly also includes embodiments in which two or more different polyether polyols (or two or more different polyester polyols, etc.) are used in the production of the polyurethane.

[0065] In a preferred embodiment of the present invention, the (b1) polyether polyol based on polyalkylene oxide comprises a polyether polyol having ethylene oxide terminals (capped), wherein the content of ethylene oxide is preferably 10-20 wt %, relative to the weight of the polyether polyol having ethylene oxide terminals.

[0066] In a preferred embodiment of the present invention, the (b1) at least one polyether polyol based on polyalkylene oxide comprises a polyether polyol based on propylene oxide and having ethylene oxide ends (capped), wherein the content of ethylene oxide is preferably 10-20% by weight, relative to the weight of the polyether polyol having ethylene oxide ends.

[0067] In a specific embodiment of the present invention, the (b1) polyether polyol based on polyalkylene oxide can be selected from one or more of the following polyether polyols and any combination thereof:

[0068] (b1-1) polyether polyol polymerized from propylene oxide with sucrose and propylene glycol as initiators; hydroxyl value of 112-450 mgKOH / g, preferably 300-400 mgKOH / g; functionality of 4-6;

[0069] (b1-2) polyether polyol prepared by polymerization of propylene oxide with sorbitol and glycerol as initiators; hydroxyl value of 112-600 mgKOH / g, preferably 450-550 mgKOH / g; functionality of 4-5.5;

[0070] (b1-3) a polyether polyol prepared by polymerization of propylene oxide with propylene glycol as an initiator; a hydroxyl value of 28-200 mgKOH / g, preferably 50-100 mgKOH / g; a functionality of 2; and

[0071] (b1-4) polyether polyol polymerized with propylene oxide using sucrose as an initiator; hydroxyl value of 112-550 mgKOH / g, preferably 400-500 mgKOH / g; functionality of 2-6, preferably 5-6;

[0072] The hydroxyl value is tested according to the method of ISO 14900-2017.

[0073] In a more preferred embodiment of the present invention, the (b1) polyether polyol based on polyalkylene oxide includes (b1-1), (b1-2) and (b1-3), wherein the amount of (b1-1) is 20-50% by weight, preferably 30-50% by weight, the amount of (b1-2) is 20-50% by weight, preferably 30-50% by weight, and the amount of (b1-3) is 10-40% by weight, preferably 20-30% by weight, based on the total weight of the (B) isocyanate-reactive component.

[0074] In a specific embodiment of the present invention, the (b1) polyether polyol based on polyalkylene oxide can be selected from one or more of the following polyether polyols and any combination thereof:

[0075] (b1-4) polyether polyol polymerized with propylene oxide using sucrose as an initiator; hydroxyl value of 112-550 mgKOH / g, preferably 400-500 mgKOH / g; functionality of 2-6, preferably 5-6;

[0076] (b1-5) a polyether polyol prepared by polymerization of propylene oxide with m-phenylenediamine as an initiator; a hydroxyl value of 112-360 mgKOH / g; a functionality of 4; and

[0077] (b1-6) polyether polyol polymerized from propylene oxide using ethylenediamine as an initiator; hydroxyl value of 112-800 mgKOH / g; functionality of 2-4;

[0078] The hydroxyl value is tested according to the method of ISO 14900-2017.

[0079] In a more preferred embodiment of the present invention, the (b1) polyether polyol based on polyalkylene oxide includes (b1-4) and (b1-5), wherein the amount of (b1-4) is 10-50% by weight, preferably 20-40% by weight, and the amount of (b1-5) is 30-90% by weight, preferably 40-60% by weight, based on the total weight of the isocyanate-reactive component (B).

[0080] In a more preferred embodiment of the present invention, the (b1) polyether polyol based on polyalkylene oxide includes (b1-4) and (b1-6), wherein the amount of (b1-4) is 10-50% by weight, preferably 20-40% by weight, and the amount of (b1-6) is 30-90% by weight, preferably 40-60% by weight, based on the total weight of the isocyanate-reactive component (B).

[0081] The functionality of the polyether polyol (b1) based on polyalkylene oxide described in the present invention is 2-10, preferably 2-6, for example 2, 3, 4, 4.5, 5, 5.8, 6, 7, 8, 9 or 10.

[0082] The hydroxyl value of the polyalkylene oxide-based polyether polyol (b1) of the present invention may be 28-800 mgKOH / g, preferably 100-500 mgKOH / g, for example 100, 310, 360, 380, 450 or 500 mgKOH / g.

[0083] In a preferred embodiment of the present invention, the content of the (b1) polyether polyol based on polyalkylene oxide can be 35%-98%, preferably 40-98%, more preferably 70-95%, based on the total weight of the (B) isocyanate reactive component and the (C) additive component.

[0084] The viscosity of the polyether polyol based on polyalkylene oxide (b1) of the present invention may be 100-20000 mPa·s, measured at 25° C. according to DIN 53019-1-3. The number average molecular weight of the polyether polyol based on polyalkylene oxide (b1) of the present invention may be 200-18000 g / mol, preferably 200-6000 g / mol, measured by gel permeation chromatography (GPC).

[0085] (b2) Polyester polyol

[0086] In one embodiment, (B) isocyanate reactive component can also optionally include polyester polyol.Polyester polyol can be aliphatic or aromatic polyester polyol, preferably aromatic polyester polyol.Polyester polyol can be prepared by reacting dicarboxylic acid or dicarboxylic acid anhydride with polyol.Dicarboxylic acid includes but is not limited to aliphatic carboxylic acid containing 2-12 carbon atoms, and the aliphatic carboxylic acid containing 2-12 carbon atoms includes but is not limited to succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecyl carboxylic acid, maleic acid, fumaric acid and its combination.Dicarboxylic acid includes but is not limited to aromatic carboxylic acid containing 6-12 carbon atoms, including but not limited to phthalic acid, isophthalic acid, terephthalic acid and its combination.The dicarboxylic acid anhydride includes but is not limited to phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride and its combination. The polyols reacted with dicarboxylic acids or dicarboxylic anhydrides include, but are not limited to, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,3-methylpropanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, glycerol, trimethylolpropane and combinations thereof. Polyester polyols may also include polyester polyols prepared from lactones. The polyester polyols prepared from lactones are preferably, but not limited to, ε-caprolactone. Polyester polyols may also include polycarbonate polyols, preferably, but not limited to, polycarbonate diols. The polycarbonate diols may be prepared by reacting diols with dialkyl or diaryl carbonates or phosgene. The diol is preferably, but not limited to, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, trioxymethylene glycol and combinations thereof. The dialkyl or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.

[0087] Preferably, the viscosity of the polyester polyol may be 200-3000 mPa·s, preferably 1000-3000 mPa·s, measured at 25° C. according to DIN 53019-1-3.

[0088] Preferably, the functionality of the polyester polyol is 2-6, preferably 2-3.

[0089] Preferably, the hydroxyl value of the polyester polyol is 100-400 mgKOH / g, preferably 200-350 mgKOH / g, for example 312 mgKOH / g.

[0090] In one embodiment of the present invention, the functionality of the polyester polyol may be 2-4, preferably 2-3, such as functionality 2, etc. The hydroxyl value of the polyester polyol may be 100-400 mgKOH / g, preferably 200-350 mgKOH / g, such as 312 mgKOH / g.

[0091] In one embodiment of the present invention, the content of the (b2) polyester polyol may be 0-20%, based on the total weight of the (B) isocyanate reactive component and the (C) additive component.

[0092] As described above, the (B) isocyanate-reactive component may optionally contain polyester polyol. That is, the content of polyester polyol may be 0%.

[0093] In a specific embodiment of the present invention, the polyester polyol can be selected from (b2-1) polyester polyols based on terephthalic acid; the hydroxyl value thereof is 28-312 mgKOH / g; and the functionality is 2.

[0094] In the present invention, the reaction between the (A) isocyanate component and the (B) isocyanate-reactive component is a polyaddition reaction between an isocyanate group and a hydroxyl group. The isocyanate group may be an isocyanate group contained in the (A) isocyanate component, or may be an isocyanate group contained in an intermediate product of the reaction between the (A) isocyanate component and the (B) isocyanate-reactive component, i.e., an isocyanate-terminated prepolymer. The hydroxyl group may be a hydroxyl group contained in the (B) isocyanate-reactive component, or may be a hydroxyl group contained in an intermediate product of the reaction between the (A) isocyanate component and the (B) isocyanate-reactive component, i.e., an isocyanate-terminated prepolymer.

[0095] In the present invention, the usage ratio of (A) isocyanate component and (B) isocyanate reactive component is mainly selected according to the equivalent ratio of the two, preferably, the molar ratio of isocyanate NCO and reactive hydroxyl OH in the polyurethane composition is 70:100-300:100.

[0096] The (C) additive component may include (c1) a catalyst, which is used to catalyze the reaction of isocyanate groups (NCO) and hydroxyl groups (OH). The catalyst can accelerate the rise of polyurethane, shorten the curing time, and improve the foaming quality. When the amount of catalyst is small, the foaming reaction rate is too low during the preparation of polyurethane foam, and the gas is difficult to escape, resulting in closed cells of polyurethane foam. As the amount of catalyst increases, the foaming reaction is accelerated and the open porosity increases; when the amount of catalyst is too large, large bubbles may appear and defects may occur due to the foaming reaction may be too fast, and even bubble collapse may occur. The amount of catalyst used will affect the properties of polyurethane foam, such as tensile strength, tear strength, etc. In the present invention, the catalyst that can be used includes but is not limited to a polyurethane equilibrium catalyst, a polyurethane foaming catalyst, or a combination thereof. The amount of the catalyst used may be 0.2-2%, preferably 0.7-1.1%, based on the total weight of the (B) isocyanate reactive component and the (C) additive component. The catalysts include (cyclo)aliphatic tertiary amine catalysts such as triethylenediamine (DABCO), methyl-diethyltriamine and N,N-dimethylcyclohexylamine, metal compounds such as dibutyltin laurate and other organic tin compounds and UL series products of Momentive Chemical Company such as UL-4, UL-6, UL-22, UL-28 and UL-32, hydroxyl-containing catalysts such as dimethylaminopropyl dipropanolamine (DPA), N-methyldiethanolamine (MDEA) and dimethylaminopropylamine (DMAPA)-Amin Z, and etheramine catalysts such as bis-N,N′-dimethylaminoethyl ether, N-ethylmorpholine (NEM) and 2,2-dimorpholinodiethyl ether (DMDEE).

[0097] The (C) additive component may include (c2) a blowing agent, the main function of which is to generate gas to form evenly distributed bubbles. The blowing agent may include water, cyclopentane blowing agent and combinations thereof. The amount of blowing agent used may be 0.3-14%, based on the total weight of the (B) isocyanate reactive component and the (C) additive component. Other available blowing agents may include, but are not limited to, fluorocarbons, hydrochlorocarbons, chlorofluorocarbons, hydrofluorocarbons and hydrocarbons. If necessary, air may be directly introduced into the system to form foam. Other suitable blowing agents may be Arkema's 365.

[0098] In one embodiment of the invention, water is used as a blowing agent, preferably in the absence of other blowing agents. The amount of water used as a blowing agent can be varied in a known manner to achieve the desired density. Suitable amounts of water are generally at least 0.3 wt %, preferably 1 to 5 wt %, based on the total weight of the (B) isocyanate-reactive component and the (C) additive component.

[0099] The (C) additive component may include (c3) a foam stabilizer, which can be used to improve the stability of bubbles generated during the preparation of polyurethane foam to improve the performance of polyurethane foam. Conventional foam stabilizers in the art can be used, such as silicone foam stabilizers, fluorine foam stabilizers and other well-known surfactants. The amount of the foam stabilizer can be 0.2-1.9%, based on the total weight of the (B) isocyanate reactive component and the (C) additive component.

[0100] The (C) additive component may include an antioxidant, which can effectively inhibit or reduce the thermal oxidation and photooxidation reaction speed of the polyurethane foam, significantly improve the heat resistance and light resistance of the polyurethane foam, delay its degradation and aging process, and thus extend the life of the polyurethane foam. Conventional antioxidants in the art can be used, including but not limited to: hindered phenol antioxidants, amine antioxidants, thio antioxidants and phosphate antioxidants.

[0101] The (C) additive component may include a color paste, which can be used to impart a suitable color to the polyurethane foam. The color paste may be added as needed to adjust the color of the polyurethane foam.

[0102] As required, the (C) additive component may also include other additives or auxiliary agents, including but not limited to: fillers, internal mold release agents, flame retardants, smoke suppressants, antistatic agents, UV stabilizers, diluents, coupling agents, surface wetting agents, leveling agents, thixotropic agents, plasticizers, foam levelers, free radical reaction inhibitors or combinations thereof.

[0103] The additives described in the present invention can be adjusted as needed, and preferably, substances with pungent odor or high volatility are not used as additives.

[0104] One or more of the additive components (C) may be optionally stored together with the isocyanate component (A), the isocyanate reactive component (B) and / or the isocyanate prepolymer. One or more of the additive components (C) may also be stored independently, and when used to prepare polyurethane foam, first mixed with the isocyanate component (A), the isocyanate reactive component (B) and / or the isocyanate prepolymer, and then used to prepare polyurethane foam.

[0105] The other foam materials described in the present invention can use any foam used as a floating material. There is no requirement for the form of the other foam materials when mixed with the polyurethane composition. Block, sheet, granular, etc. can be used. There is no effect on the performance of the finally obtained floating material. The size of the other foam materials can be 0.1 mm-12 cm, and 0.1 mm-5 cm granular other foam materials are preferably used. The other foam materials can be, for example, one or more of polystyrene (EPS) foam materials, polyolefin foam materials, polyester foam materials and combinations thereof. The polyolefin foam material can be a polyethylene foam material, preferably a high-density polyethylene (HDPE) foam material. The polyester foam material can be a polyethylene terephthalate (PET) foam material.

[0106] The other foam materials described in the present invention are preferably recycled foam materials. Other foam materials salvaged from water bodies can be directly used in the present invention without the need for an additional drying step.

[0107] The present invention has no special requirements for the performance of other foam materials. The apparent density of the other floating materials can be 10-45 kg / m3, preferably 10-20 kg / m3.

[0108] The mass ratio of other foam materials to polyurethane foam materials described in the present invention is greater than or equal to 1:9, for example 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, etc., preferably greater than or equal to 3:7, to obtain better performance.

[0109] In the floating material of the present invention, the polyurethane foam is usually a continuous phase and other foam materials are a dispersed phase.

[0110] The shell material of the present invention can be selected from commonly used plastic shell materials, such as one or more of polyolefin, polystyrene, polycarbonate, polyester and polyamide, preferably polyolefin, more preferably polyethylene. The wall thickness of the shell material is preferably 0.1-5mm, so as to achieve good contact and tightness with the polyurethane foam, good mechanical properties and floating properties.

[0111] In the present invention, the other foam materials are at least partially wrapped by the polyurethane foam, preferably completely wrapped by the polyurethane foam, and more preferably dispersed in the polyurethane foam and completely wrapped by the polyurethane foam.

[0112] The polyurethane foam described in the present invention is wrapped by the shell material, preferably completely wrapped by the shell material or the shell material covers at least 90% of the surface area of ​​the polyurethane foam, preferably more than 95%.

[0113] The shell material of the present invention may include a closable opening for allowing the polyurethane composition and other foam materials to enter the shell material. The opening is preferably a switchable opening.

[0114] The shell material of the present invention can be selected in various shapes, such as bag-shaped, box-shaped, cocoon-shaped, barrel-shaped, bottle-shaped, strip-shaped, block-shaped, etc. The shell material can be a hard shell material or a soft shell material.

[0115] The volume of the shell material of the present invention is preferably 10 cm 3 -10m 3 .

[0116] The floating material of the present invention may further include a reinforced mesh bag outside the shell material, which is used to surround the shell material. The reinforced mesh bag may be made of conventional plastic mesh bag material, such as polypropylene and / or nylon, preferably polypropylene.

[0117] The polyurethane foam of the present invention may have the following properties:

[0118] Cream time, 5 seconds to 2 minutes; Cream time refers to the time difference from the start of mixing of the polyol-containing component and the polyisocyanate component (counted as 0 seconds) to the time when the polyurethane composition begins to turn creamy white.

[0119] Foam gel time 30 seconds to 15 minutes; Foam gel time refers to the time from the start of mixing of the polyol-containing component and the polyisocyanate component (counted as 0 seconds) to the time period for the polyurethane composition to cure (until the composition begins to become viscous when touched with a stick-like solid).

[0120] The free foam density is 15-500 kg / m3, preferably 20-300 kg / m3, more preferably 25-200 kg / m3, most preferably 20-50 kg / m3; tested according to ISO 845.

[0121] Compression strength 100-500kPa;

[0122] No particles will fall off due to external friction.

[0123] In the present invention, components (A) and (B) in the polyurethane composition need to be stored separately before use. The storage conditions of component (C) are not limited, and it can be stored separately from component (A) and component (B), or stored together with component (A) or component (B), or a part of component (C) can be stored with component (A), and the other part of component (C) can be stored with component (B).

[0124] In one embodiment of the present invention, component (A) and component (B) are stored in a package having a divider, and the package is stored in the shell material.

[0125] The present invention also provides a method for preparing the floating material, which comprises the following steps: mixing and foaming the polyurethane composition and the other foam materials in the shell material, and sealing the shell material before the polyurethane foam overflows from the shell material.

[0126] The other foam materials may be recycled other foam materials, which do not need to be dried and can be directly used for the preparation.

[0127] There is no particular requirement for the order of mixing components (A), (B) and (C) of the polyurethane composition with other foams. For example, the components of the polyurethane composition may be mixed first and then mixed with other foam materials, or any two or more components of the polyurethane composition may be mixed first and then mixed with other components and then mixed with other foam materials, or any one or more components of the polyurethane composition may be mixed first with other foam materials and then with other components.

[0128] The appropriate mixing order can be selected according to actual conditions. In a preferred embodiment of the present invention, other foam materials are added to the shell material before the polyurethane composition.

[0129] In another preferred embodiment of the present invention, the other foam material is added to the shell material no later than at least one component of the polyurethane composition.

[0130] In another preferred embodiment of the present invention, other foam materials are already added to the shell material before being mixed with the polyurethane composition.

[0131] Preferably, after the other foam materials and the polyurethane composition are mixed, the housing is shaken or stirred to facilitate sufficient foaming.

[0132] In the present invention, the foaming temperature is not particularly limited, and conventional ambient temperature can meet the temperature requirement for foaming, such as 0-40°C, preferably room temperature 15-25°C.

[0133] In a preferred embodiment of the present invention, the method for preparing the floating material comprises the following steps: adding other foam materials into the shell material, adding all components of the polyurethane composition into the shell material, sealing the opening of the shell material, and shaking the shell material.

[0134] In one embodiment of the present invention, the method for preparing the floating material comprises the following steps: (1) adding other foam materials into a shell material, wherein the shell material comprises the polyurethane composition stored in a packaging bag, and the packaging bag comprises a partition to separate component (A) and component (B); (2) removing the partition and stirring component (A) and component (B); (3) sealing the opening of the shell material and shaking the shell material.

[0135] Beneficial Effects

[0136] After the polyurethane composition used in the floating material of the present invention is prepared in situ, it can form a high mechanical strength, low density foam as a whole, and after mixing with other foam materials, a floating material with low density, high mechanical strength and high durability is obtained. The floating material can be directly used as a floating material for aquatic product farming. The floating material of the present invention has a long service life and will not break into waters during use to affect the water environment.

[0137] The floating material of the present invention can be prepared on-site at the recycling site of other foam materials or floating materials, and the obtained floating material can be directly put into use, saving transportation, time and labor costs. The shell of the floating material of the present invention can be used as both a shell of the floating material and a storage container of the polyurethane composition, which is more conducive to transportation and storage.

[0138] Example

[0139] The present invention will be further described below in conjunction with specific examples. However, it should be understood that these examples are only used to illustrate the present invention and do not constitute a limitation to the scope of the present invention.

[0140] The test methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise specified, all percentages and parts are by weight. Unless otherwise specified, various raw materials and equipment used in this article are commercially available.

[0141] Materials and reagents

[0142] Polyethylene hollow float (commercially available product) (produced by Ningbo Xiangyu Plastic Co., Ltd.)

[0143] PET hollow float (commercial product) (Taizhou Huangyan Xianwei Plastic Machinery Co., Ltd.) wall thickness is 5mm

[0144] Styrene foam-Type I: Recycled styrene foam, density 18.4kg / m 3 (contrast)

[0145] Styrene Foam-Type II: Recycled Styrene Foam, density 14.5kg / m 3 (contrast)

[0146] Desmodur 44V20L: polymeric diphenylmethane diisocyanate, solid content 100 wt%, isocyanate group content 30.5±0.5 wt% (relative to the total mass of Desmodur 44V20L), viscosity 200±60 mPa·s (25° C.); available from Covestro Polymers (China) Co., Ltd.

[0147] DC 380, a polyether polyol prepared by polymerization of propylene oxide with sucrose and propylene glycol as initiators; hydroxyl value 380 mgKOH / g; functionality 5.8; viscosity 12000 mPa·s (25°C); available from Jurong Ningwu New Materials Development Co., Ltd.

[0148] NJ 635, a polyether polyol prepared by polymerization of propylene oxide with sorbitol and glycerol as initiators; hydroxyl value 500 mgKOH / g; functionality 4.5; viscosity 5800 mPa·s (25° C.); available from Jurong Ningwu New Materials Development Co., Ltd.

[0149] NJ 210, a polyether polyol prepared by polymerization of propylene oxide with propylene glycol as an initiator; hydroxyl value 100 mgKOHg / : functionality 2, viscosity 160 mPa·s (25° C.); available from Jurong Ningwu New Materials Development Co., Ltd.

[0150] NJ 4502, a polyether polyol prepared by polymerization of propylene oxide with sucrose as the initiator; hydroxyl value 450 mgKOH / g; functionality 5-6; viscosity 17250 mPa·s (25°C); available from Jurong Ningwu New Materials Development Co., Ltd.

[0151] Stepanpol 3152, terephthalic acid-based polyester polyol; hydroxyl value 312 mgKOH / g; functionality 2; viscosity 2500 mPa·s (25° C.); available from Nanjing Stepan Company.

[0152] Arcol 1362, a polyether polyol polymerized with propylene oxide using glycerol as an initiator and having ethylene oxide as the terminal group; hydroxyl value 28; ethylene oxide content 20% by weight; functionality 3; available from Covestro Polymers (China) Co., Ltd.

[0153] DESMOPHEN 24HK69, a polyether polyol prepared by polymerization of propylene oxide with m-phenylenediamine as the initiator; hydroxyl value 360 ​​mgKOHg; functionality 4; viscosity 17250 mPa·s (25°C); available from Covestro Polymers (China) Co., Ltd.

[0154] DMCHA: dimethylcyclohexylamine; polyurethane equilibrium catalyst, purchased from Jinan Mingxin Chemical Co., Ltd.

[0155] PC 5: Pentamethyltriethylenediamine: polyurethane foaming catalyst, available from Momentive Corporation.

[0156] CP foaming agent: commercially available cyclopentane foaming agent.

[0157] Diethanolamine, ethanolamine: common commercial chemicals.

[0158] L 6920: Polyurethane rigid foam stabilizer, available from Momentive Corporation.

[0159] HYPERLITE 1650 was purchased from Covestro.

[0160] DABCO 33LV LIQUID was purchased from Air Products.

[0161] TEGOSTAB B 4690 polyurethane flexible foam stabilizer is available from Degussa.

[0162] The viscosity of the above raw materials is measured at 25° C. according to DIN 53019-1-3. The isocyanate NCO% content is measured according to GB / T12009.4-2016.

[0163] Test method:

[0164] Cream time: the time difference from the start of mixing of the isocyanate-reactive component and the isocyanate component (counted as 0 seconds) to the time when the polyurethane composition starts to turn creamy white.

[0165] Gel time: The time from the start of mixing of the isocyanate-reactive component and the isocyanate component (counted as 0 seconds) to the time period during which the polyurethane composition is cured (the time until the composition starts to become viscous when touched with a stick-like solid).

[0166] Tack-free time: The time elapsed from the mixing of the isocyanate-reactive component and the isocyanate component until the foam surface no longer feels tacky.

[0167] Foam free rise density: tested according to ISO845.

[0168] Compression Strength: Tested according to ASTM D1621.

[0169] Molded foam density was tested according to ASTM C303.

[0170] Floating ability in water: throw the floating material into the water, the more the part exposed above the water after reaching balance, the better the floating ability, which is divided into three levels: general (+++), good (++++) and very good (+++++).

[0171] Shell impact test: A square wood (5cm*5cm*5cm) weighing 20 kg is freely dropped from a height of 1 meter above the shell to impact the shell.

[0172] Friction experiment: Tie a 5-kg weight to one end of a polypropylene rope and hold the other end with your hand. Rub the rope back and forth on the floating material at a speed of 3 meters per minute. After rubbing it 10 times, observe the degree of wear of the floating material.

[0173] Polyurethane system formula PU-1

[0174] Table 1 Isocyanate reactive components

[0175]

[0176] The polyurethane system material PU-1 is obtained by mechanically stirring and mixing the isocyanate reactive components shown in Table 1 and polymeric MDI Desmodur44V20L in a ratio of 100 parts by weight: 155 parts by weight. The milky time of the reaction system is 45 seconds; the gel time is 200 seconds; and the non-stick time is 320 seconds. The free foaming density of the foam is 40kg / m 3 The system can be operated for more than 3 minutes.

[0177] Polyurethane system formula PU-2

[0178] Table 2: Isocyanate-reactive components

[0179] Isocyanate reactive component (B) Content (parts by weight) Stepanpol 3152 Polyester polyols 20 NJ 4502 Polyether polyol (sucrose) 30 24HK69 Polyether polyol (m-phenylenediamine) 50 L 6920 Foam stabilizer 2 DMCHA Polyurethane Equilibrium Catalyst 0.8 PC 5 Polyurethane foaming catalyst 0.5 water Foaming agent 3.4

[0180] The polyurethane system material PU-2 is obtained by mixing the isocyanate reactive components shown in Table 2 with polymeric MDI Desmodur44V20L in a ratio of 100 parts by weight to 116 parts by weight, and adding 13 parts by weight of foaming agent CP. The milky time of the reaction system is 5 seconds; the gel time is 36 seconds; and the non-stick time is 46 seconds. The free foaming density of the foam is 25 kg / m 3 The system can be operated within 36 seconds. PU-2 is a fast-response system suitable for high-volume machining.

[0181] Polyurethane system formula PU-3

[0182] Table 3: Isocyanate-reactive components

[0183] Isocyanate reactive component (B) Content (parts by weight) Arcol 1362 Polyether polyols 64.8 HYPERLITE 1650 Polymer polyether 27.7 DMCHA catalyst 0.32 DABCO 33LV LIQUID catalyst 0.23 Diethanolamine Crosslinking agent 0.46 Ethylene glycol Chain Extender 2.70 TEGOSTAB B 4690 Foam stabilizer 0.37 PC 5 catalyst 0.14 water Foaming agent 0.32

[0184] The polyurethane system material PU-3 is obtained by mixing the isocyanate reactive components shown in Table 3 with polymeric MDI Desmodur44V20L in a ratio of 30 parts by weight to 100 parts by weight, and adding 12 parts by weight of foaming agent CP. The milky time of the reaction system is 48 seconds; the gel time is 84 seconds; and the non-stick time is 120 seconds. The free foaming density of the foam is 80 kg / m 3 The system can be operated within 45 seconds. PU-3 is a fast-response system suitable for high-volume machining.

[0185] Examples 1-14 and Comparative Examples 1-5

[0186] Tables 4 and 5 list the raw materials and performance comparisons of the floating materials made according to Examples 1-14 and Comparative Examples 1-5.

[0187] Comparative Example 1 is a traditional sea and river surface aquaculture float, which is made of low-density polystyrene plastic foam-type I plus a polypropylene mesh bag. It is light in weight, has high buoyancy and is very easy to operate, but has low strength and is easily broken. The general service life is only about three years, which is the main cause of coastal pollution.

[0188] Comparative Example 2 is a commercial polyethylene hollow float. In order to ensure strength and buoyancy, the commercial polyethylene hollow shell is very thick, so the float weight and volume are 20-30% larger than the traditional styrene foam float. Once the polyethylene hollow shell is punctured, the polyethylene hollow float will leak and partially sink, and can no longer meet the float buoyancy performance requirements.

[0189] Comparative Example 3 is a commercial polyester hollow float. The commercial polyester hollow float is very thin and has very good buoyancy, but the shell is very brittle and easily punctured. During the installation process, about 20% of the shells usually break. After the shell breaks, it will leak water and sink, and it can no longer meet the buoyancy performance requirements of the float.

[0190] Comparative Example 4 is to mix the traditional sea and river surface aquaculture float, low-density polystyrene foam-type I (90 weight%) with polyurethane system material PU-1 (10 weight%), and put it into a thin layer of polyethylene hollow shell (wall thickness 2mm). Its weight is lighter than the polyethylene hollow float and its density is about 23.1kg / m 3 , it is very easy to operate with large buoyancy, but its strength is low, with a compression strength of 125kPa. Moreover, the low-density polystyrene plastic foam and polyurethane foam are not completely bonded and mixed together. Once the polyethylene hollow shell is punctured, the polyethylene hollow shell float will leak, partially sink, lose some buoyancy, and no longer meet the float buoyancy performance requirements.

[0191] Embodiment 1 is to break up the traditional sea and river surface aquaculture float, low-density polystyrene foam-type I, and mix and foam 80% by weight of this material with 20% by weight of polyurethane foam formula PU-1 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is very easy to operate, and the compression strength is increased to 155kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured, the hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0192] Embodiment 2 is to break up the traditional sea and river surface aquaculture float, low-density polystyrene plastic foam-type I, and mix and foam 70% by weight of this material with 30% by weight of polyurethane foam formula PU-1 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is very easy to operate. The compression strength is increased to 190kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured, the hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0193] Embodiment 3 is to break up the traditional sea and river surface aquaculture float, low-density polystyrene plastic foam-type I, and mix and foam 60% by weight of this material with 40% by weight of polyurethane foam formula PU-1 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has sufficient buoyancy and is very easy to operate. The compression strength is increased to 222kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured, the hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0194] Embodiment 4 is to break up the traditional sea and river aquaculture float, low-density polystyrene plastic foam-type I, and mix and foam 40% by weight of this material with 60% by weight of polyurethane foam formula PU-1 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is very easy to operate. The compression strength is increased to 288kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured, the hollow shell float will not leak and will not sink; it continues to maintain buoyancy, and can fully meet the float buoyancy performance requirements.

[0195] Embodiment 5 is to break up the traditional sea and river surface aquaculture float, low-density polystyrene plastic foam-type I, and mix and foam 20 weight % of this material with 80 weight % of polyurethane foam formula PU-1 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is very easy to operate. The compression strength is increased to 356kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured, the polyethylene hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0196] Example 6 is to put the polyurethane foam formula PU-1 (100%) into a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell after foaming. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is easy to operate. The foam compression strength is increased to 425kPa. Even if the polyethylene hollow shell is punctured, the polyethylene hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0197] Table 5 lists the performance comparison of the floats of the polyurethane system PU-2 with different contents of low-density styrene foam materials.

[0198] Comparative Example 5 is a traditional sea and river surface aquaculture float, which is made of low-density polystyrene plastic foam-type II plus a polypropylene mesh bag. The obtained product has a large buoyancy and is very easy to operate. However, it has low strength and is easily broken; its general service life is only about three years, which is the main cause of coastal pollution at present. It is the main target of the present invention.

[0199] Example 7 is to break up the traditional sea and river aquaculture float, low-density polystyrene plastic foam-type II, and mix and foam 80% by weight of this material with 20% by weight of polyurethane foam formula PU-2 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is very easy to operate. The compression strength is increased to 112kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured; the polyethylene hollow shell float does not leak, does not sink; continues to maintain buoyancy; and can fully meet the float buoyancy performance requirements.

[0200] Example 8 is to break up the traditional sea and river aquaculture float, low-density polystyrene plastic foam-type II, and mix and foam 70% by weight of this material with 30% by weight of polyurethane foam formula PU-2 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is very easy to operate. The compression strength is increased to 133kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured; the polyethylene hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0201] Embodiment 9 is to break up the traditional sea and river surface aquaculture float, low-density polystyrene plastic foam-type II, and mix and foam 60% by weight of this material with 40% by weight of polyurethane foam formula PU-2 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has sufficient buoyancy and is very easy to operate. The compression strength is increased to 154kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured, the polyethylene hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0202] Embodiment 10 is to break up the traditional sea and river surface aquaculture float, low-density polystyrene plastic foam-type II, and mix and foam 50% by weight of this material with 50% by weight of polyurethane foam formula PU-2 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has a density of, has large buoyancy and is very easy to operate. The compression strength is increased to 175kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured, the polyethylene hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0203] Example 11 is to break up the traditional sea and river aquaculture float, low-density polystyrene plastic foam-type II, and mix and foam 40% by weight of this material with 60% by weight of polyurethane foam formula PU-2 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is very easy to operate. The compression strength is increased to 196kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured; the polyethylene hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0204] Example 12 is to break up the traditional sea and river aquaculture float, low-density polystyrene plastic foam-type II, and mix and foam 30% by weight of this material with 70% by weight of polyurethane foam formula PU-2 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is very easy to operate. The compression strength is increased to 217kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured; the polyethylene hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0205] Embodiment 13 is to break up the traditional sea and river surface aquaculture float, low-density polystyrene plastic foam-type II, and mix and foam 80% by weight of this material with 20% by weight of polyurethane foam formula PU-2 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is very easy to operate. The compression strength is increased to 238kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured, the polyethylene hollow shell float will not leak, will not sink, and will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0206] Example 14 is to break up the traditional sea and river surface aquaculture float, low-density polystyrene plastic foam-type II, and mix and foam 40% by weight of this material with 60% by weight of polyurethane foam formula PU-3 in a thin layer of polyethylene hollow shell (thickness 2mm), and then seal the shell. The obtained product is lighter than the polyethylene hollow shell, has large buoyancy and is very easy to operate. The compression strength is increased to 160kPa. The low-density polystyrene plastic foam and the polyurethane foam are completely bonded and mixed into one. Even if the polyethylene hollow shell is punctured, the hollow shell float will not leak or sink; it will continue to maintain buoyancy, which can fully meet the float buoyancy performance requirements.

[0207] From the results in Table 4 and Table 5, it can be seen that the use of the polyurethane foam material of the present invention or its combination with various styrene foam materials can obtain a float product with excellent properties, such as low density, high buoyancy and high mechanical strength. Under the condition of equivalent density, by increasing the content of the polyurethane foam material, a composite material with better performance can be obtained. In particular, when the content of the polyurethane foam material of the present invention in the float material product is higher than 10% by weight, preferably higher than 20% by weight, more excellent performance can be obtained.

[0208] Although the specific embodiments of the present invention are described above, it should be understood by those skilled in the art that this is only for illustration and the protection scope of the present invention is defined by the appended claims. Those skilled in the art may make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but these changes and modifications all fall within the protection scope of the present invention.

[0209]

[0210]

Claims

1. A floating material comprising polyurethane foam, other foam materials different from polyurethane foam, and A shell material wrapping the polyurethane foam, wherein the other foam material is at least partially wrapped by the polyurethane foam, the mass ratio of the other foam material to the polyurethane foam material is greater than or equal to 1:9, and the other foam material includes one or more of polyolefin foam material, polystyrene foam material, polyester foam material and any combination thereof; the polyurethane foam is made of a polyurethane composition, and the polyurethane composition includes (A) an isocyanate component, (B) an isocyanate reactive component and (C) an additive, wherein (A) an isocyanate component comprising at least one polyisocyanate; (B) an isocyanate-reactive component comprising: (b1) at least one polyether polyol based on polyalkylene oxide, having a hydroxyl value of 100 to 500 mgKOH / g and a functionality of 2 to 10, Optionally (b2) at least one polyester polyol; (C) The additive component comprises one or more of the following: (c1) a catalyst; (c2) a blowing agent; (c3) Foam stabilizer.

2. The floating material according to claim 1, characterized in that: The (b1) at least one polyether polyol based on polyalkylene oxide, whose initiator is a polyhydroxy compound, or a combination of a polyhydroxy compound and a polyamine; the polyhydroxy compound is preferably selected from one or more of sorbitol, sucrose, propylene glycol, glycerol, ethylene glycol, 1,2-propylene glycol, diethylene glycol, trimethylolpropane, bisphenol A, bisphenol S and a combination thereof, more preferably selected from one or more of sucrose, propylene glycol, sorbitol, glycerol and a combination thereof; the polyamine is preferably selected from one or more of ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, toluenediamine, meta-phenylenediamine and a combination thereof, more preferably selected from meta-phenylenediamine and / or ethylenediamine.

3. The floating material according to claim 2, characterized in that: The (b1) at least one polyalkylene oxide-based polyether polyol is selected from one or more of the following polyether polyols and any combination thereof: (b1-1) polyether polyol polymerized from propylene oxide with sucrose and propylene glycol as initiators; hydroxyl value of 112-450 mgKOH / g, preferably 300-400 mgKOH / g; functionality of 4-6; (b1-2) polyether polyol prepared by polymerization of propylene oxide with sorbitol and glycerol as initiators; hydroxyl value of 112-600 mgKOH / g, preferably 450-550 mgKOH / g; functionality of 4-5.5; (b1-3) polyether polyol obtained by polymerization of propylene oxide with propylene glycol as initiator; hydroxyl value of 28-200 mgKOH / g, preferably 50-100 mgKOH / g; functionality of 2; and (b1-4) polyether polyol polymerized with propylene oxide using sucrose as an initiator; hydroxyl value of 112-550 mgKOH / g, preferably 400-500 mgKOH / g; functionality of 2-6, preferably 5-6; or The polyether polyol is selected from the following polyether polyols and any combination thereof: (b1-4) polyether polyol polymerized with propylene oxide using sucrose as an initiator; hydroxyl value of 112-550 mgKOH / g, preferably 400-500 mgKOH / g; functionality of 2-6, preferably 5-6; (b1-5) a polyether polyol prepared by polymerization of propylene oxide with m-phenylenediamine as an initiator; a hydroxyl value of 112-360 mgKOH / g; a functionality of 4; and (b1-6) polyether polyol polymerized from propylene oxide using ethylenediamine as an initiator; hydroxyl value of 112-800 mgKOH / g; functionality of 2-4; or The polyether polyol comprises at least one polyether polyol based on polyalkylene oxide, which has ethylene oxide terminal, wherein the content of ethylene oxide is 10-20% by weight relative to the weight of the polyether polyol.

4. The floating material according to any one of claims 1 or 2, characterized in that: The hydroxyl value of the polyether polyol based on polyalkylene oxide (b1) is 28-800 mgKOH / g, preferably 100-500 mgKOH / g; the functionality of the polyether polyol based on polyalkylene oxide (b1) is 2-10, preferably 2-6; the functionality of the at least one polyester polyol (b2) is 2-6, preferably 2-3; or the hydroxyl value of the at least one polyester polyol (b2) is 100-400 mgKOH / g, preferably 200-350 mgKOH / g.

5. The floating material according to any one of claims 1 to 4, characterized in that: The content of the (b1) polyether polyol is 35%-98%, preferably 40-98%, more preferably 70-95%, based on the total weight of the (B) isocyanate reactive component and the (C) additive component; The content of the (b2) polyester polyol is 0-20% by weight, based on the total weight of the (B) isocyanate reactive component and the (C) additive component.

6. The floating material according to any one of claims 1 to 5, characterized in that: The isocyanate NCO% content in the (A) isocyanate component is 5-33.6%, preferably 10-32%, based on the total weight of the isocyanate component, measured in accordance with GB / T 12009.4-2016.

7. The floating material according to any one of claims 1 to 6, characterized in that: The (A) isocyanate component includes at least one polyisocyanate, and the polyisocyanate is selected from one or more of toluene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, methylcyclohexyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, polymers thereof and combinations thereof.

8. The floating material according to any one of claims 1 to 7, characterized in that: The functionality of the polyisocyanate is 2.0-3.5, preferably 2.1-2.9; the viscosity of the polyisocyanate is 5-700 mPa·s, preferably 10-300 mPa·s, more preferably 100-300 mPa·s, measured at 25° C. according to DIN 53019-1-3.

9. The floating material according to any one of claims 1 to 8, characterized in that: The (A) isocyanate component includes 4,4'-diphenylmethane diisocyanate and / or polyphenylmethane polyisocyanate; the isocyanate component preferably includes more than 95%, preferably more than 97% of 4,4'-diphenylmethane diisocyanate; or the isocyanate component preferably includes more than 95%, preferably more than 97% of polyphenylmethane polyisocyanate; calculated by weight percentage of the (A) isocyanate component.

10. The floating material according to any one of claims 1 to 9, characterized in that: The molar ratio of isocyanate NCO to reactive hydroxyl OH in the polyurethane composition is 70:100-300:

100.

11. The floating material according to any one of claims 1 to 10, characterized in that: The other foam materials are polystyrene foam materials, polyolefin foam materials, polyester foam materials and combinations thereof; the shell material is one or more of polyolefin, polystyrene, polycarbonate, polyester and polyamide; the wall thickness of the shell material is 0.1-5mm.

12. A method for preparing a floating material as claimed in any one of claims 1 to 11, comprising the following steps: mixing and foaming the polyurethane composition and the other foam materials in the shell material, and sealing the shell material before the polyurethane foam overflows from the shell material.

13. The preparation method according to claim 12, characterized in that: The other foam materials are recycled other foam materials, which do not need to be dried and can be directly used for the preparation.

14. The preparation method according to claim 12 or 13, characterized in that: The method comprises the following steps: (1) adding other foam materials into a shell material, wherein the shell material contains the polyurethane composition stored in a packaging bag, wherein the packaging bag has a partition to separate component (A) and component (B); (2) removing the partition and stirring component (A) and component (B); (3) sealing the opening of the shell material and shaking the shell material.

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