Radix asparagi polyurea composition with low free diisocyanate content as well as preparation method and application of radix asparagi polyurea composition

Abstract

The invention discloses an asparagus polyurea composition with low free diisocyanate content as well as a preparation method and an application of the asparagus polyurea composition. The composition comprises a component A and a component B, the component A is prepared from the following raw materials in parts by mass: 55 to 65 parts of hexamethyl diisocyanate derivative, 25 to 35 parts of low-free polyfunctional allophanate polymer, 5 to 10 parts of filler and 0.1 to 1 part of additive; the component B is prepared from the following raw materials in parts by mass: 90 to 95 parts of radix asparagi resin, 5 to 10 parts of filler and 0.1 to 1 part of additive. According to the formula scheme that the low-free polyfunctional allophanate polymer and the HDI tripolymer are used in a combined mode, the concentration of the free diisocyanate monomer can be reduced to 0.1 wt% or below, and the polyurethane sealant has the advantages of being good in miscibility, stability, water resistance and the like, is used in the field of sealant and can achieve product environment protection and healthy construction.

Description

Technical Field

[0001] The invention relates to an aspartame polyurea composition with low free diisocyanate content, a preparation method and application thereof, and belongs to the field of aspartame polyurea resin preparation. Background Art

[0002] Aliphatic isocyanate prepolymers and HDI polymers have good yellowing resistance. The asparagine polyurea materials prepared by reacting them with aspartic acid ester resins have very good toughness and strength as well as excellent yellowing resistance and chemical resistance. The prepolymer provides toughness and the HDI polymer provides strength. Asparagine polyurea is a good choice for high-quality household caulking materials. Because it involves household use and a wide range of construction groups, environmental protection and safety need to be paid special attention. The latest REACH regulations stipulate that the concentration of diisocyanate monomers shall not exceed 0.1% (by weight) whether used alone or in combination. Therefore, low-free diisocyanate asparagine polyurea caulking agent is very necessary.

[0003] At present, the preparation technology of asparagus polyurea seam beautifying agent products, in which the isocyanate component is mainly composed of high-free difunctional isocyanate prepolymers, combined with HDI trimer, such as patents CN 110317528 A and CN 116120819A. In such a combination, the free monomers in the difunctional prepolymers are relatively high, resulting in poor environmental protection, often causing allergies, irritation and other problems. The solution is to physically remove the free monomers to achieve environmental protection, but the prepolymer after the monomer is removed has particularly poor miscibility with the HDI trimer and cannot be used.

[0004] In actual formulation operation, the miscibility of low-free prepolymer and HDI trimer is particularly poor, and whitening or even stratification will occur. Due to uneven mixing, it cannot be cured and ultimately cannot be used. Therefore, in the preparation of low-free multifunctional allophanate polymer, how to achieve good miscibility with HDI trimer is a technical problem that urgently needs to be solved in this field. Summary of the invention

[0005] In order to overcome the shortcomings of the prior art, the present invention provides an asparagine polyurea composition with low free diisocyanate and a preparation method thereof, which can reduce the concentration of free diisocyanate monomers to below 0.1wt% (1000ppm) through the formulation of low free multifunctional allophanate polymer and HDI trimer, and has good miscibility, stability, water resistance and other advantageous properties.

[0006] The present invention also provides application of the aspartame polyurea composition with low free diisocyanate in the field of seam beautifying agents, which can achieve environmentally friendly products and healthy construction.

[0007] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0008] The present invention provides an aspartame polyurea composition with low free diisocyanate content, comprising component A and component B;

[0009] The A component includes the following raw materials in parts by weight:

[0010] 55-65 parts of hexamethyl diisocyanate derivatives, such as 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, etc.,

[0011] 25-35 parts of low free multifunctional allophanate polymer, such as 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, etc.,

[0012] 5-10 parts of filler, such as 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.,

[0013] 0.1-1 part of auxiliary agent, for example, 0.1 part, 0.3 part, 0.5 part, 0.7 part, 0.9 part, 1 part, etc.;

[0014] The B component includes the following raw materials in parts by weight:

[0015] 90-95 parts of asparagus resin, such as 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, etc.,

[0016] 5-10 parts of filler, such as 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.,

[0017] 0.1-1 part of auxiliary agent, for example, 0.1 part, 0.3 part, 0.5 part, 0.7 part, 0.9 part, 1 part, etc.;

[0018] The molar ratio of the component A, calculated based on the isocyanate groups (-NCO) therein, to the component B, calculated based on the secondary amine groups (-NH-), is 1-1.1:1.

[0019] In one embodiment, the hexamethyl diisocyanate derivative of component A is selected from one or more of hexamethyl diisocyanate trimer and hexamethyl diisocyanate biuret, and more preferably Wanhua HT-600, HT-300, HT-400, and HB-200.

[0020] In one embodiment, the low free multifunctional allophanate polymer of component A has a free diisocyanate monomer content of ≤0.1wt%; for example, 0.1wt%, 0.09wt%, 0.08wt%, 0.07wt%, 0.06wt%, 0.05wt%, 0.04wt%, 0.03wt%, 0.02wt%, 0.01wt%, 0.005wt%, etc.

[0021] The multifunctional allophanate polymer described in the present invention is a product disclosed in the prior art, and there is no special requirement for its source. It can be a common commercially available product purchased, or a product prepared by technicians based on existing processes. For example, the polymer can be prepared by the following methods listed in the present invention:

[0022] Specifically, the low-free polyfunctional allophanate polymer is prepared by firstly performing a prepolymerization reaction of a diisocyanate and a macromolecular polyol to generate a carbamate prepolymer, then performing a polymerization reaction to generate an allophanate structure, and then removing unreacted diisocyanate monomers to obtain an isocyanate-terminated low-free polyfunctional allophanate polymer; wherein the unreacted diisocyanate monomers are removed to reduce the free diisocyanate monomer content therein to ≤0.1wt%;

[0023] Preferably, the diisocyanate is selected from aliphatic diisocyanates, preferably one or more of isophorone diisocyanate (IPDI), (4,4-dicyclohexylmethane diisocyanate) HMDI, (hexamethylene diisocyanate) HDI, (xylylene diisocyanate) XDI, (cyclohexane dimethylene diisocyanate) HXDI;

[0024] Preferably, the macromolecular polyol has a molecular weight of 600-6000 and is selected from polyether polyols (such as Wanhua C2020, F3135), polyester polyol (such as Wanhua Wanthanol WHP-208), polycaprolactone polyol (such as Polyren PCL-3057), polycarbonate polyol (such as Wanhua WANTHANCOL@WHP-CD100), one or more thereof, more preferably C2020, F3135

[0025] Preferably, the mass ratio of the diisocyanate to the macromolecular polyol is 1:1.8-3;

[0026] Preferably, the prepolymerization temperature is 60-70°C; the end point of the prepolymerization is when the theoretical NCO reaches 8.3-9.5%; the theoretical NCO content is a conventional means in the field to determine the end point of the reaction of isocyanate and polyol, and can be calculated by technicians based on the effective content ratio of isocyanate and polyol;

[0027] Preferably, the polymerization reaction temperature is 70-120°C and the time is 1-4h;

[0028] In addition, a catalyst may be added during the reaction. The specific type and amount are not required. The catalyst may be conventionally selected in the field. For example, the prepolymerization catalyst may be dibutyltin dilaurate, bismuth isooctanoate, stannous octoate, etc.; the polymerization reaction catalyst may be bismuth carboxylate, potassium carboxylate, zirconium carboxylate, etc.

[0029] The above-mentioned method for preparing allophanate by reacting diisocyanate with polyol is a conventional process in the field. Other related operations and process conditions involved, and the devices used therein, can be carried out by conventional selection in the field. There is no special restriction on this. Technicians can optimize it according to actual needs based on the known processes in the prior art, which will not be repeated here.

[0030] In one embodiment, the low free polyfunctional allophanate polymer of component A has an isocyanate group (—NCO) content of 5.5-6.31 wt %.

[0031] In one embodiment, the total isocyanate group (—NCO) content of the A component is 14-15.5 wt %.

[0032] In one embodiment, the asparagine resin of component B is selected from one or more of 4,4'-diaminodicyclohexylmethane asparagine resin, 3,3'-dimethyl-4,4-diaminodicyclohexylmethane asparagine resin, and polyetheramine asparagine resin; for example,

[0033] The 4,4'-diaminodicyclohexylmethane type asparagine resin may be one or more of N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester and N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetrabutyl ester;

[0034] The 3,3'-dimethyl-4,4-diaminodicyclohexylmethane type asparagine resin can be N,N'-(methylenedi-(1-methyl, -4,1-cyclohexanediyl) diaspartic acid tetraethyl ester);

[0035] The polyetheramine type asparagine resin is an asparagine resin prepared from polyetheramine, and can be prepared using polyetheramines of different molecular weights such as D230, T403, etc. For example, polyether type asparagine resins F2850, F330, etc. produced by Zhuhai Feiyang can be used.

[0036] In one embodiment, the fillers in component A and component B are selected from one or more of hydrophobic fumed silica, hydrophilic fumed silica, bentonite, etc., preferably hydrophobic fumed silica. The fillers in component A and component B may be the same or different.

[0037] In one embodiment, the addition of the auxiliary agent to component A and component B is a conventional operation method in the field. The auxiliary agent includes one or more of a defoamer, a dispersant, and a substrate wetting agent. The auxiliary agents in component A and component B may be the same or different. The auxiliary agents may be selected conventionally in the field. The present invention has no special requirements. For example,

[0038] The defoamer is selected from one or more of BYK-085, BYK-072, and BYK-065;

[0039] The dispersant is selected from one or more of BYK-164, BYK-9076, and BYK-180;

[0040] Preferably, based on 0.1-1 part of the auxiliary agent in component A, the defoamer accounts for 0.1-0.5 part and the dispersant accounts for 0.1-0.5 part;

[0041] Preferably, based on 0.1-1 part of the auxiliary agent in the B component, the defoaming agent accounts for 0.1-0.5 part and the dispersant accounts for 0.1-0.5 part.

[0042] The invention provides a method for preparing the aspartame polyurea composition with low free diisocyanate.

[0043] The method for preparing the aspartame polyurea composition with low free diisocyanate content is to obtain component A and component B respectively by conventional physical blending, and specifically, the steps include:

[0044] The hexamethyl diisocyanate derivative, the low-free multifunctional allophanate polymer, the filler and the additive are uniformly mixed to obtain component A;

[0045] The asparagus resin, filler and additives are uniformly mixed to obtain component B.

[0046] The present invention also provides the use of the aspartame polyurea composition with low free diisocyanate as mentioned above.

[0047] The low-free diisocyanate aspartame polyurea composition, in which the free diisocyanate monomer concentration is reduced to below 0.1wt%, has the advantages of being non-irritating, yellowing-resistant, and environmentally friendly, and is suitable for use in the fields of seam beautifiers, sealants, and flooring, and is particularly suitable for use as a seam beautifier.

[0048] Among them, when using the asparagine polyurea caulking agent with low free diisocyanate, component A and component B are respectively injected into the two-component caulking agent tube, and the construction operation can be carried out.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] The free diisocyanate content in component A is low, which can reduce the risk of allergies, benefit the occupational hygiene of end operators, comply with regulatory requirements, and improve the miscibility, stability, water resistance and other related properties of component A. It can achieve full curing when used as a caulking agent. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 This is the stability picture of component A in Example 2 after storage for 24 hours;

[0052] Figure 2 This is a picture of the components of component A in comparative example 3 after mixing;

[0053] Figure 3 This is a stability picture of component A in comparative example 3 after storage for 24 hours. DETAILED DESCRIPTION

[0054] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0055] In the examples and comparative examples of the present invention, the sources of the main raw materials used are as follows. Unless otherwise specified, other raw materials and reagents are purchased from commercial sources: hexamethylene diisocyanate (HDI), from Wanhua Chemical Group Co., Ltd.;

[0056] Isophorone diisocyanate (IPDI), Wanhua Chemical;

[0057] Dicyclohexylmethane diisocyanate (HMDI), Wanhua Chemical;

[0058] 1,3-Di(isocyanatomethyl)cyclohexane (H6XDI), Wanhua Chemical;

[0059] Meta-phenylenedimethyl isocyanate (XDI), Wanhua Chemical;

[0060] Polyether polyol (C2020), molecular weight 2000, Wanhua Chemical;

[0061] Polyester polyol (WHP-208), molecular weight 2000, Wanhua Chemical;

[0062] Hexamethyl diisocyanate trimer (HT-600), Wanhua Chemical;

[0063] Hexamethyl diisocyanate biuret (HB-200), Wanhua Chemical;

[0064] Dibutyltin dilaurate (T12) was purchased from Beijing Inokai Technology Co., Ltd.;

[0065] Bismuth carboxylate (Valikat Bi2010) was purchased from Umicore;

[0066] N,N'-(methylenedi-4,1-cyclohexanediyl) diaspartic acid tetraethyl ester (F421) was purchased from Zhuhai Feiyang New Materials Co., Ltd.;

[0067] N,N'-(methylenedi-(1-methyl,-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester) (F520) was purchased from Zhuhai Feiyang New Materials Co., Ltd.;

[0068] Polyetheramine type asparagine resin (F2850) was purchased from Zhuhai Feiyang New Materials Co., Ltd.;

[0069] Fumed silica (fumed silica) (A200) was purchased from Wanhua Tianhe.

[0070] Preparation Example 1-10:

[0071] Low free polyfunctional allophanate polymer samples 1-10 were prepared as follows:

[0072] According to the raw material formula in Table 1 below, diisocyanate was added to a 1L four-necked flask, the oil bath temperature was controlled at 60°C, 0.02g of dibutyltin dilaurate was added, and a large molecular weight polyol was added dropwise by a peristaltic pump. After the theoretical NCO reached 9.45%, 0.1g of catalyst bismuth carboxylate (8210) was added, and the reaction was carried out at 80°C for about 4h, and the reaction was stopped. The unreacted diisocyanate monomer was removed by a thin film evaporator to obtain a low-free multifunctional allophanate polymer. The free diisocyanate monomer content and the isocyanate group (-NCO) content were tested, and the NCO content was tested using a potentiometric titrator, and the results are shown in Table 1.

[0073] Table 1 Raw material formula and test results of low free polyfunctional allophanate polymer samples 1-10

[0074]

[0075] [Examples 1-10]

[0076] According to the raw material formula in Table 2 below, a low-free diisocyanate aspartame polyurea composition was prepared:

[0077] The hexamethyl diisocyanate derivative, the low-free multifunctional allophanate polymer, the filler, the defoamer and the dispersant are uniformly mixed to obtain component A;

[0078] The hexamethyl diisocyanate derivative, the low-free multifunctional allophanate polymer, the filler, the defoamer and the dispersant are uniformly mixed to obtain component B.

[0079] Table 2 Raw material formula of Examples 1-10

[0080]

[0081]

[0082] Comparative Example 1

[0083] 101 g of hexamethylene diisocyanate (HDI) was added into a 1 L four-necked flask, the oil bath temperature was controlled at 60°C, 0.02 g of dibutyltin dilaurate was added, and 300 g of polyether polyol C2020 was added dropwise via a peristaltic pump. After the theoretical NCO reached 9.45%, the reaction was stopped to obtain a high free urethane prepolymer with a free monomer content of 15 wt%.

[0084] The formulation of Example 1 is followed, except that the low-free polyfunctional allophanate polymer sample 1 is replaced with an equal amount of the above-mentioned high-free urethane prepolymer, and other conditions remain unchanged.

[0085] Comparative Example 2

[0086] 101 g of hexamethylene diisocyanate (HDI) was added into a 1 L four-necked flask, the oil bath temperature was controlled at 60°C, 0.02 g of dibutyltin dilaurate was added, 300 g of polyether polyol C2020 was added dropwise by a peristaltic pump, and the reaction was stopped after the theoretical NCO reached 9.45%, and the unreacted HDI monomer was removed by a thin film evaporator to obtain a low-free urethane prepolymer, wherein the free monomer content was <0.05 wt%.

[0087] The formulation of Example 1 is followed, except that the low-free polyfunctional allophanate polymer sample 1 is replaced with an equal amount of the above-mentioned low-free urethane prepolymer, and other conditions remain unchanged.

[0088] Comparative Example 3

[0089] 134 g of isophorone diisocyanate (IPDI) was added into a 1 L four-necked flask, the oil bath temperature was controlled at 60°C, 0.02 g of dibutyltin dilaurate was added, 300 g of polyether polyol C2020 was added dropwise by a peristaltic pump, and the reaction was stopped after the theoretical NCO reached 8.77%, and the unreacted IPDI monomer was removed by a thin film evaporator to obtain a low-free urethane prepolymer, wherein the free monomer content was <0.09 wt%.

[0090] The formulation of Example 1 is followed, except that the low-free polyfunctional allophanate polymer sample 1 is replaced with an equal amount of the above-mentioned low-free urethane prepolymer, and other conditions remain unchanged.

[0091] Test Example 1:

[0092] Taking the component A prepared in Example 2 and Comparative Example 3 as an example, its miscibility and stability were tested:

[0093] Figure 1 This is a stability picture of component A in Example 1 after storage for 24 hours. It is a clear and transparent liquid with good miscibility and remains stable after long storage, proving that it has good storage stability.

[0094] Figure 2 This is a picture of the ingredients of component A in comparative example 3 after mixing. After mixing, it is white and turbid, and the miscibility is poor.

[0095] Figure 3 This is a stability picture of component A in comparative example 3 after storage for 24 hours. The sample is stratified and has poor stability. When used as a caulking agent, it will not be able to cure in the end due to uneven mixing.

[0096] Test Example 2:

[0097] The asparagus polyurea seam beautifying agent compositions with low free diisocyanate prepared in Examples 1-10 and Comparative Examples 1-3 were used as asparagus polyurea seam beautifying agents and were subjected to performance tests.

[0098] Component A and component B were injected into the two-component seam sealant tube respectively, and the following method was used to test the complete curing time and water resistance. The results are shown in Table 23:

[0099] Water absorption test: Take about 10g of the dried caulking agent sample and soak it in water for 24 hours to test the water absorption rate before and after soaking;

[0100] Curing test: Touch with your finger to feel whether the surface is dry and sticky.

[0101] Table 3 Performance test results

[0102]

[0103]

[0104] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be regarded as the scope of protection of the present invention.

Claims

1. A low-free diisocyanate aspartame polyurea composition, characterized in that: It includes component A and component B; The A component includes the following raw materials in parts by weight: 55-65 parts of hexamethyl diisocyanate derivatives, 25-35 parts of low free multifunctional allophanate polymer, 5-10 parts of filler, Additives 0.1-1 part; The B component includes the following raw materials in parts by weight: 90-95 parts of asparagus resin, 5-10 parts of filler, Additives 0.1-1 part; The molar ratio of the component A, calculated based on the isocyanate groups therein, to the component B, calculated based on the secondary amine groups therein, is 1-1.1:

1.

2. The aspartame polyurea composition with low free diisocyanate content according to claim 1, characterized in that: The hexamethyl diisocyanate derivative is selected from one or more of hexamethyl diisocyanate trimer and hexamethyl diisocyanate biuret.

3. The aspartame polyurea composition with low free diisocyanate content according to claim 1, characterized in that: The low-free polyfunctional allophanate polymer of component A has a free diisocyanate monomer content of ≤0.1 wt%.

4. The aspartame polyurea composition with low free diisocyanate content according to claim 1 or 3, characterized in that: The low-free polyfunctional allophanate polymer is prepared by firstly performing a prepolymerization reaction of diisocyanate and a macromolecular polyol to generate a carbamate prepolymer, then performing a polymerization reaction to generate an allophanate structure, and then removing unreacted diisocyanate monomers to obtain an isocyanate-terminated low-free polyfunctional allophanate polymer; wherein the unreacted diisocyanate monomers are removed to reduce the free diisocyanate monomer content therein to ≤0.1wt%.

5. The aspartame polyurea composition with low free diisocyanate content according to claim 4, characterized in that: The diisocyanate is selected from aliphatic diisocyanates, preferably one or more of isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and cyclohexane dimethylene diisocyanate; and / or The molecular weight of the macromolecular polyol is 600-6000; the molecular weight of the macromolecular polyol is preferably one or more of polyether polyol, polyester polyol, polycaprolactone polyol and polycarbonate polyol; and / or The mass ratio of the diisocyanate to the macromolecular polyol is 1:1.8-3; and / or The prepolymerization temperature is 60-70°C; The prepolymerization reaction ends when the theoretical NCO reaches 8.3-9.5%; and / or The polymerization reaction temperature is 70-120° C. and the reaction time is 1-4 hours.

6. The aspartame polyurea composition with low free diisocyanate content according to claim 1, characterized in that: The isocyanate content of the low free multifunctional allophanate polymer in component A is 5.5-6.31 wt %; and / or The total isocyanate content of the A component is 14-15.5 wt %.

7. The aspartame polyurea composition with low free diisocyanate content according to claim 1, characterized in that: The asparagine resin is selected from one or more of 4,4'-diaminodicyclohexylmethane type asparagine resin, 3,3'-dimethyl-4,4-diaminodicyclohexylmethane type asparagine resin, and polyetheramine type asparagine resin; Preferably, the 4,4'-diaminodicyclohexylmethane type asparagine resin is one or more of N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetraethyl ester and N,N'-(methylenedi-4,1-cyclohexanediyl)diaspartic acid tetrabutyl ester; Preferably, the 3,3'-dimethyl-4,4-diaminodicyclohexylmethane type asparagine resin is N,N'-(methylenebis-(1-methyl,-4,1-cyclohexanediyl) diaspartic acid tetraethyl ester).

8. The aspartame polyurea composition with low free diisocyanate content according to claim 1, characterized in that: The filler is selected from one or more of hydrophobic fumed silica, hydrophilic fumed silica, and bentonite, preferably hydrophobic fumed silica; and / or The auxiliary agent includes one or more of a defoamer, a dispersant, and a substrate wetting agent.

9. A method for preparing the aspartame polyurea composition with low free diisocyanate content according to any one of claims 1 to 8, characterized in that the steps include: The hexamethyl diisocyanate derivative, the low-free multifunctional allophanate polymer, the filler and the additive are uniformly mixed to obtain component A; The asparagus resin, filler and additives are uniformly mixed to obtain component B.

10. Use of the asparagine polyurea composition with low free diisocyanate content according to any one of claims 1 to 8 or the asparagine polyurea composition with low free diisocyanate content prepared by the method according to claim 9 in the fields of seam beautifiers, sealants, and flooring, especially as seam beautifiers.

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