Special cross-linking agent for soft polyurethane foam and application of special cross-linking agent

Abstract

The invention relates to the technical field of cross-linking agents, in particular to a special cross-linking agent for soft polyurethane foam, which comprises the following components in percentage by mass: 1-85% of alkyl glycoside compound, 1-5% of polyoxyethylene propylene ether compound, 1-5% of urea derivative, 1-5% of stabilizer of urea derivative and the balance of solvent. The polyoxyethylene propylene ether compound accounts for 1-40% of the cross-linking agent; the urea derivative accounts for 1-25% of the cross-linking agent; the stabilizer accounts for 0.01 to 1 percent of the cross-linking agent; and the solvent accounts for 1-40% of the cross-linking agent. When the cross-linking agent adopting the formula is used in the production process of polyurethane foam, rapid cross-linking curing in the early stage of foaming can be helped, foam opening is promoted, the problem of cold deformation bulging of high resilience of large foam blocks is solved, meanwhile, the use amount of diethanol amine is reduced, and the hardness problem of soft foam caused by diethanol amine can be solved.

Description

Technical Field

[0001] The invention relates to the technical field of crosslinking agents, in particular to a special crosslinking agent for soft polyurethane foam and application thereof. Background Art

[0002] Polyurethane is a general term for polymer compounds containing repeated carbamate groups on the main chain. Soft polyurethane foam is a particularly important type of polyurethane material. It has good resilience and load-bearing capacity and is widely used as furniture, sound insulation, filtration and lining materials.

[0003] Soft polyurethane foam is generally divided into ordinary polyurethane soft foam, high-resilience foam and slow-resilience foam. High-resilience foam has high resilience and explosive power and is widely used in car seat cushions, sofas and mattresses. The polyether polyol used in TDI system high-resilience foam is generally EO-terminated. The produced pore diameters are mixed and distributed, and the skeleton thickness is different. When the load is compressed, it will produce different supporting forces under different deformation states. TDI system high-resilience foam has excellent rebound, good cushioning and shock absorption and foam durability. It is an ideal material for providing high-end cushion products and furniture pads. In the actual production process of large-block high-resilience foam, stannous octoate is used as a gel-type catalyst, and the problem of cold deformation shrinkage bulging of the foam or local shrinkage depression in the foam often occurs, which is difficult to solve even by rolling and exhausting. Organic tin compounds can coordinate with isocyanate to polarize ─NCO, thereby making the positively charged carbon atoms in the isocyanate molecule more active and more susceptible to attack by the terminal hydroxyl groups of the polyol polymer. In the early production of large-scale high-resilience foam, dibutyltin dilaurate was used as a gel-type catalyst. The dibutyltin dilaurate structure has large steric hindrance, the gel selectivity is not strong, the dosage is small, and the dosage of amine catalyst in the formula is high, which can quickly promote the reaction between water and isocyanate to release aromatic amino groups. The aromatic amino group has strong reactivity and helps to quickly cure and cross-link to form a more stable structural solidified foam. The aromatic amino group continues to react with isocyanate to form urea groups, which promotes foam opening, thus preventing foam cooling shrinkage and foam bulging. Dibutyltin dilaurate is highly toxic when inhaled, and is highly toxic to aquatic organisms, and can have long-term adverse effects on the aquatic environment.

[0004] To this end, patent document US4211849A discloses a method for producing polyurethane foam, using high-functionality alcohol to help initial cross-linking, and the resulting foam shows a very small proportion of closed cells, with extremely high elasticity and flexibility values, preventing the foam from shrinking after production. Patent CN102395613B discloses a polyurethane foam composition and a method for making polyurethane foam, using N-hexyldiethanolamine, diisopropanolamine, γ-aminopropyltriethoxysilane, 2-methyl-1,3-propylene glycol and polyoxyethylene glycol glycerol ether, and then introducing acid to control the effect of cross-linking on the reaction rate, helping to improve the foam connectivity of molded high-resilience foam, and increase production tolerance and qualified rate. Summary of the invention

[0005] The object of the present invention is to provide a special crosslinking agent for soft polyurethane foam to solve the problem of cold deformation and bulging of large-block high-resilience foam caused by using stannous octoate.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A special crosslinking agent for flexible polyurethane foam, comprising an alkyl glycoside compound, wherein the alkyl glycoside compound accounts for 1-85% of the crosslinking agent by mass percentage;

[0008] The invention comprises a polyoxyethylene propylene ether compound, wherein the polyoxyethylene propylene ether compound accounts for 1-40% of the cross-linking agent by mass percentage, and the polyoxyethylene propylene ether compound has the following structural formula:

[0009] R[(CH2CH2O) n (CHCH3CH2O) m ] x H(1)

[0010] Wherein, R is one or more of sorbitol, mannitol, lactitol, erythritol, glucose, and sucrose, n=0-10; m=0-10; x=6-10;

[0011] comprising a urea derivative, wherein the urea derivative accounts for 1-25% of the cross-linking agent by mass percentage;

[0012] A stabilizer comprising a urea derivative, wherein the stabilizer accounts for 0.01-1% of the cross-linking agent by mass percentage;

[0013] The solvent is included, and the solvent accounts for 1-40% of the cross-linking agent by mass percentage.

[0014] Preferably, in the structural formula of the polyoxyethylene propylene ether compound, n=0-3; m=0-3.

[0015] As a specific embodiment, the alkyl glycoside compound is selected from one or more of methyl glucoside, n-octyl glucoside, decyl glucoside, lauryl glucoside, C8-10 alkyl glucoside, C8-14 alkyl glucoside, C12-14 alkyl glucoside, tetradecyl glucoside, polyol glucoside, N-dodecyl glucoside lauramide, N-hydroxyethyl lauryl glucoside, n-octyl-β-pyranoglucoside, nonyl-β-D-pyranoglucoside, glucosamine lauramide, fatty alcohol lactose monoglycoside, and fatty alcohol lactose diglycoside.

[0016] As a specific embodiment, the urea derivative is selected from at least one of hydroxymethyl urea, trimethylol urea, hydroxyethyl urea, hydroxymethyl urea, urea hydrochloride, semicarbazide hydrochloride, and urea.

[0017] As a specific implementation, the solvent is selected from one or more of double distilled water, diethylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, ethylene glycol, 1,4-butanediol, glycerol, trimethylolpropane, and pentaerythritol.

[0018] As a specific embodiment, the special cross-linking agent for flexible polyurethane foam also includes a stabilizer for urea derivatives, which mainly provides alkalinity to help stabilize the urea derivatives. The urea derivative stabilizer is selected from triethylenediamine, pentamethylenetriamine, dimethylaminopropylamine diisopropyl alcohol, pentamethyldiethylenetriamine, tetramethyldipropylenetriamine, N,N-dimethyl-1,3-diaminopropane, 3-dimethylaminopropyl urea, (dimethylaminoethyl) ether, N,N-di[3-(dimethylamino)propyl]-N',N'-dimethyl-1,3-propylenediamine, hexadecylamine, 2-[[3-(dimethylamino)propyl]methylamino]ethanol, 1,3,5-tris(dimethylaminopropyl)-1,3, 5-Hexahydrotriazine, N,N-dimethylethanolamine, N,N-dimethylbenzylamine, triethanolamine, diethanolamine, 1,8-diazabicyclo[5,4,0]undec-7-ene, 6-dimethylamino-1-hexanol, N-methyldicyclohexylamine, hexadecylamine, tetramethylguanidine, ammonia water, 1-isobutyl-2-methylimidazole, 2-amino-α-[[2-(1,1-dimethylethoxy)-2-oxoethoxy]imino]-4-thiazoleacetic acid, O,O-diethylthiophosphate anhydride, N-ethylmorpholine, N-methylmorpholine, benzylamine, diethylaminoethanol, N,N'-diisopropylcarbodiimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 1,2-dimethylimidazole oxazole, N-methylimidazole, 2,2-dimorpholinyl diethyl ether, dimethylaminoethoxyethanol, 2-dimethylaminopyridine, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2-methylaminopyridine, 4-dimethylaminopyridine, 2,4-bis(dimethylamino)pyrimidine-6-carboxylic acid, 1-(methylamino)-3-(4-methylpiperazin-1-yl)-2-propanol, aminopiperazine hydrochloride, 2,2,4-trimethyl-2-silamorpholine, 1-(2-dimethylaminoethyl)piperazine, 1-(3-dimethylaminopropyl)piperazine, (2-morpholinopyridin-4-yl)methylamine, 4-chloro-6-dimethylaminopyrimidine, N,N-dimethyl(morpholin-2-yl)formamide, N,N-dimethyl(R- One or more of the following: morpholin-2-yl)formamide, 4-methylmorpholine-2-methylamine, N,N-dimethyl(4-methyl-1-piperazinyl)ethylamine, hexahydro-1,3,5-trimethyl-S-triazine, 1,3,5-triethylhexahydro-S-triazine, N,N'-carbonyldiimidazole, dicyclohexylcarbodiimide, 3-(diethoxyphosphoryloxy), 2-(7-azobenzotriazole)-N,N,N',N'-tetramethyluronium hexafluorophosphate, N-hydroxy-7-azobenzotriazole, tripyrrolidinylphosphonium bromide hexafluorophosphate, O-benzotriazole-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(N-succinimide)-1,1,3,3-tetramethyluronium tetrafluoroborate.

[0019] Another object of the present invention is to provide the use of the above-mentioned special cross-linking agent for soft polyurethane foam in the preparation of polyurethane high-resilience foam, polyurethane slow-resilience foam and special polyurethane foam.

[0020] By means of the above technical scheme, the present invention provides a special crosslinking agent for soft polyurethane foam, which has the following beneficial effects: the crosslinking agent of the present invention simultaneously introduces alkyl glycoside nonionic surfactants containing 4 primary alcohols, multifunctional polyoxyethylene propylene ether, and urea derivatives, and these structures contain primary alcohol hydroxyl groups and primary amino groups with higher reactivity, and react with isocyanate first in the reaction process of preparing polyurethane foam, capture more isocyanate, and cause the hard segment to quickly aggregate to form an independent microphase region, increase the microphase separation of the foam structure, and help obtain a more open-cell high-resilience foam. At the same time, the crosslinking speed of the foam is increased to help solidify the foam, obtain a drier side, and prevent the cold deformation bulging of the foam, solve the problem of cold deformation bulging of large-block high-resilience foam caused by using stannous octoate, and have good crosslinking stability, which can reduce the amount of diethanolamine used and increase the hardness of the foam. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a picture of a polyurethane foam plastic product prepared using the formula of the standard sample of Comparative Example 1;

[0022] Figure 2 This is a diagram of a polyurethane foam product to which 1.2 parts of the cross-linking agent prepared in Example 3 is added. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0024] Example 1

[0025] This embodiment provides a special crosslinking agent for flexible polyurethane foam, which is obtained by uniformly mixing 30g of C8-10 alkyl glucoside 0810, 40g of sorbitol polyoxyethylene ether (Mn=1121), 20g of trimethylol urea, 9.95g of double distilled water and 0.05g of ammonia water at room temperature. In this embodiment, C8-10 alkyl glucoside 0810 contains 50wt% of double distilled water.

[0026] Example 2

[0027] This embodiment provides a special crosslinking agent for flexible polyurethane foam, which is obtained by uniformly mixing 30g of C8-10 alkyl glucoside 0810, 40g of sorbitol polyoxyethylene ether (Mn=1121), 20g of urea hydrochloride, 9.95g of double distilled water and 0.05g of ammonia water at room temperature. In this embodiment, C8-10 alkyl glucoside 0810 contains 50wt% of double distilled water.

[0028] Example 3

[0029] This embodiment provides a special crosslinking agent for flexible polyurethane foam, which is obtained by uniformly mixing 30g of C8-10 alkyl glucoside 0810, 40g of lactitol polyoxyethylene ether (Mn=1000), 20g of semicarbazide hydrochloride, 9.95g of double distilled water and 0.05g of ammonia water at room temperature. In this embodiment, C8-10 alkyl glucoside 0810 contains 50wt% of double distilled water.

[0030] Test 1

[0031] The polyurethane foam is prepared by the following steps:

[0032] The polyurethane soft foam formula is shown in Table 1 by using the standard sample of Example 1-3 with 1.2 parts added and the standard sample of Comparative Example 1 without adding the crosslinking agent for comparison.

[0033] Table 1

[0034]

[0035]

[0036] Weigh the materials as shown in Table 1 into a stirring kettle, stir at 25°C at a stirring speed of 2100 rpm / min for 5 seconds, pour into a foaming box until the reaction is completed, and record the bubble jumping time to obtain a polyurethane foam plastic.

[0037] It should be noted that polyether polyol 330N comes from Jiangsu Changhua Polyurethane Co., Ltd., polymer polyol H45 comes from Jiangsu Changhua Polyurethane Co., Ltd., UF-5366, A-33, A-1 and T-9 come from Jiangsu Aoshijia Material Technology Co., Ltd., toluene diisocyanate TDI comes from Huntsman Polyurethane Co., Ltd., and the special cross-linking agent prepared in Examples 1, 2 and 3 contains 25% of water, which needs to be deducted when calculating the formula addition.

[0038] The density of the samples was tested according to the national standard GB6343-1995; the elongation and tear strength of the samples were tested according to the national standard GB / T6344-1996 for soft polyurethane foam plastics; the rebound rate of the samples was tested according to the national standard GB / T6770-2008 for soft polyurethane foam plastics; the indentation hardness of the samples was tested according to the method B of the national standard GB / T10807-2006 for soft polyurethane foam plastics. The results are shown in Table 2:

[0039] Table 2

[0040]

[0041]

[0042] Test 2

[0043] The following steps are used to prepare polyurethane foam:

[0044] The polyurethane soft foam formula is shown in Table 3 by using the standard sample of Example 1-3 with 1.5 parts of the above examples 1-3 and the comparative example 2 without adding the crosslinking agent for comparison.

[0045] Table 3

[0046]

[0047]

[0048] Weigh the materials as shown in Table 3 into a stirring kettle, stir them at 25°C at a stirring speed of 2100 rpm / min for 5 seconds, pour them into a foaming box until the reaction is completed, and record the bubble jumping time to obtain polyurethane foam plastics.

[0049] It should be noted that polyether polyol 330N comes from Jiangsu Changhua Polyurethane Co., Ltd., polymer polyol H45 comes from Jiangsu Changhua Polyurethane Co., Ltd., UF-5366, A-33, A-1 and T-9 come from Jiangsu Aoshijia Material Technology Co., Ltd., toluene diisocyanate TDI comes from Huntsman Polyurethane Co., Ltd., and the special cross-linking agent prepared in Examples 1-3 contains 25% of water, which needs to be deducted when calculating the formula addition.

[0050] The density of the samples was tested according to the national standard GB6343-1995; the elongation and tear strength of the samples were tested according to the national standard GB / T6344-1996 for soft polyurethane foam plastics; the resilience of the samples was tested according to the national standard GB / T6770-2008 for soft polyurethane foam plastics; the indentation hardness of the samples was tested according to the method B of the national standard GB / T10807-2006 for soft polyurethane foam plastics. The results are shown in Table 4:

[0051] Table 4

[0052] D25 Comparative Example 2 Standard Sample Example 1 Example 2 Example 3 Jump bubble time / s 204 233 231 235 Density / (Kg / m3) 37.99 38.78 38.48 38.05 Rebound / % 52 55 54 57 25% indentation hardness / N 120.02 130.58 131.88 132.61 40% indentation hardness / N 164.96 172.49 175.37 178.56 65% indentation hardness / N 286.61 296.91 301.04 301.77 Air permeability (L / min) 68.22 90.93 98.6 94.44 Comfort Factor 2.39 2.27 2.28 2.275

[0053] It can be seen from Table 2 and Table 4 that by comparing the air permeability data of Examples 1-3 and the comparative standard samples, it is found that compared with the comparative standard samples, the soft polyurethane foams prepared in Examples 1-3 have better open cell performance, and the compression hardness of the sponge is increased. This is because the special cross-linking agent used in the formula reduces the amount of DEOA. DEOA contains a secondary amine, which reacts with isocyanate first, and then the two primary alcohols react with isocyanate, which hinders the formation of hydrogen bonds in the hard segment region, resulting in soft foam. The addition of the special cross-linking agent will not hinder the formation of hydrogen bonds in the hard segment region, but will help increase the hydrogen bonds in the hard segment, which is beneficial to the foam opening and increasing the foam compression hardness.

[0054] The formulations of Comparative Sample 1 and Example 3 were selected to produce large-block high-resilience foams to test the effect of the special cross-linking agent in preventing the foam from cold deformation and bulging. Figure 1 and 2 shown. Figure 2 After adding 1.2 parts of special cross-linking agent and reducing the amount of DEOA, the side aging speed increased significantly, and the foam did not show cold deformation and bulging.

[0055] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0056] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A special crosslinking agent for soft polyurethane foam, characterized in that: Including alkyl glycoside compounds, in terms of mass percentage, the alkyl glycoside compounds account for 1-85% of the cross-linking agent; The invention comprises a polyoxyethylene propylene ether compound, wherein the polyoxyethylene propylene ether compound accounts for 1-40% of the cross-linking agent by mass percentage, and the polyoxyethylene propylene ether compound has the following structural formula: R [(CH2CH2O) n (CHCH3CH2O) m ] x H (1) Wherein, R is one or more of sorbitol, mannitol, lactitol, erythritol, glucose, and sucrose, n=0-10; m=0-10; x=6-10; Including urea derivatives, the urea derivatives account for 1-25% of the cross-linking agent by mass percentage; A stabilizer comprising a urea derivative, wherein the stabilizer accounts for 0.01-1% of the cross-linking agent by mass percentage; Including the solvent, the solvent accounts for 1-40% of the cross-linking agent by mass percentage.

2. The special crosslinking agent for flexible polyurethane foam according to claim 1, characterized in that: In the structural formula of the polyoxyethylene propylene ether compound, n=0-3; m=0-3.

3. The special crosslinking agent for flexible polyurethane foam according to claim 1, characterized in that: The alkyl glycoside compound is selected from one or more of methyl glucoside, n-octyl glucoside, decyl glucoside, lauryl glucoside, C8-10 alkyl glucoside, C8-14 alkyl glucoside, C12-14 alkyl glucoside, tetradecyl glucoside, polyol glucoside, N-dodecyl glucoside lauramide, N-hydroxyethyl lauryl glucoside, n-octyl-β-pyranoglucoside, nonyl-β-D-pyranoglucoside, glucosamine lauramide, fatty alcohol lactose monoglycoside, and fatty alcohol lactose diglycoside.

4. The special crosslinking agent for flexible polyurethane foam according to claim 1, characterized in that: The urea derivative is selected from at least one of hydroxymethyl urea, trimethylol urea, hydroxyethyl urea, hydroxymethyl urea, urea hydrochloride, semicarbazide hydrochloride and urea.

5. The special crosslinking agent for flexible polyurethane foam according to claim 1, characterized in that: The solvent is selected from one or more of double distilled water, diethylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, ethylene glycol, 1,4-butanediol, glycerol, trimethylolpropane, and pentaerythritol.

6. Use of the special cross-linking agent for soft polyurethane foam according to any one of claims 1 to 5 in the preparation of polyurethane high-resilience foam, polyurethane slow-resilience foam and special polyurethane foam.

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