A non-foaming polyurethane composition, its preparation method and application

Abstract

This invention relates to the field of new materials technology, and discloses a non-foaming polyurethane composition, its preparation method, and its application. The non-foaming polyurethane composition is prepared from the following components: Component I is an -NCO-terminated prepolymer oligomer obtained by prepolymerization of diisocyanate and oligomeric polyol; Component P1 includes oligomeric polyol, catalyst, antioxidant and anti-yellowing agent, anti-hydrolysis agent, and antistatic agent; Component P2 is a chain extender; the mass ratio of Component I, Component P1, and Component P2 is 1:P1:P2 = 100:(40-70):(3-8). The polyurethane composition of this invention, obtained by mixing Component I, Component P1, and Component P2 in a preset ratio, mold casting, and medium-temperature (80°C) molding process, has the properties of long working time, easy mold filling, fast molding and demolding, non-foaming, high transparency, high wear resistance, hydrolysis resistance, and antistatic properties, and is also environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of new materials technology, specifically to a non-foaming polyurethane composition, its preparation method, and its application. Background Technology

[0002] Polyurethane polymer materials are widely used, and my country has become the world's largest polyurethane production base, with rapid development in the application of polyurethane materials. Polyurethane foam materials are used in shoe soles, especially sports shoe soles, and have many years of mature application experience. However, the application of non-foamed polyurethane shoe sole materials is still in a slow development process, mainly because rubber or PVC non-foamed shoe sole materials occupy a large share of the low-to-mid-end market due to their price advantage. Nevertheless, polyurethane materials have excellent wear resistance, flexibility, and flexural properties, and are often used in high-end shoe soles.

[0003] In recent years, shoe styles and trends have changed rapidly, especially for novel trendy shoes suitable for young people. Transparent soles have also become a novel trendy element in high-end footwear design. Currently, the high-end non-foamed transparent wear-resistant polyurethane sole composite materials on the market still have shortcomings in terms of processability and physical properties. Specifically, these include short processing time, slow demolding, difficulty in controlling air bubbles in the finished product, low scrap rate, and poor hydrolysis and wear resistance.

[0004] For example, existing technology discloses a high-transparency, high-bending-resistance mirror-like polyurethane resin, its preparation method, and its applications. This high-bending-resistance, high-transparency mirror-like polyurethane resin is prepared using components comprising the following weight percentages: 6-25% polyester diol, 2-5% chain extender, 10-15% diisocyanate, 0.02-0.05% antioxidant, 0.05-0.25% end-capping agent, and the balance being solvent. The polyester diol is selected from one or more of poly(1,4-butanediol adipate), poly(1,6-hexanediol adipate), poly(neoprenediol adipate), poly(1,4-butanediol adipate), or poly(1,6-hexanediol adipate). The high-bending-resistance, high-transparency mirror-like polyurethane resin obtained by this technology can be used to prepare shoe uppers.

[0005] In the medium-temperature molding process of polyurethane, catalysts are commonly used to shorten the molding time. Currently, most catalysts widely used in polyester-type polyurethane materials are based on tertiary amines, such as triethylenediamine-based composite catalysts like Evonik's DABCO 33LV and KTM60. While these catalysts are effective in curing MDI polyester materials, they suffer from insufficient catalytic targeting and sensitivity to trace amounts of moisture. In particular, small-molecule alcohol chain extenders in the material, including hydrophilic alcohols such as ethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, are prone to absorbing water. During the curing process, they inevitably catalyze the reaction of isocyanates with trace amounts of moisture to generate CO2, leading to defects such as bubbles, flakes, and cracks after molding, affecting appearance and mechanical properties, and resulting in a high scrap rate. Summary of the Invention

[0006] To address the aforementioned technical problems, the present invention provides a non-foaming polyurethane composition;

[0007] Another object of the present invention is to provide a method for preparing a non-foaming polyurethane composition;

[0008] Another object of the present invention is to provide an application of a non-foaming polyurethane composition.

[0009] This invention provides the following technical solution:

[0010] A non-foaming polyurethane composition is prepared from the following components:

[0011] Component I is an -NCO-terminated prepolymer oligomer obtained by prepolymerization of diisocyanate and oligomeric polyol;

[0012] Component P1 includes oligomeric polyols, catalysts, antioxidants and anti-yellowing agents, anti-hydrolysis agents, and antistatic agents;

[0013] Component P2 is a chain extender;

[0014] The mass ratio of component I, component P1, and component P2 is I:P1:P2 = 100:(40-70):(3-8).

[0015] Preferably, the diisocyanate in component I is 4,4'-diphenylmethane diisocyanate or carbodiimide-modified 4,4'-diphenylmethane diisocyanate. More preferably, the diisocyanate in component I is 4,4'-diphenylmethane diisocyanate.

[0016] Preferably, the oligomeric polyol in component I is a polyester polyol with a hydroxyl value of 53-59 (mgKOH / g).

[0017] More preferably, the polyester polyol in component I is poly(neoprene adipate) diol.

[0018] Preferably, the mass ratio of diisocyanate to polyester polyol in component I is (30-35):(65-70), and the NCO value is 7-8.

[0019] Preferably, the oligomeric polyol in component P1 is selected from any one or a mixture of two of polyester polyols or polyether polyols.

[0020] Preferably, the polyester polyol in component P1 is polypentyl adipate diol with a hydroxyl value of 53-59 (mgKOH / g); the polyether polyol is polytetrahydrofuran diol with a hydroxyl value of 53-59 (mgKOH / g).

[0021] Preferably, the catalyst in component P1 is a bimetallic catalyst, and the amount added is 0.1-0.5% of the mass of component P1. The bimetallic catalyst has the characteristics of targeted catalysis of isocyanate and hydroxyl reactions, and is insensitive to and does not catalyze trace amounts of moisture in the material. It avoids CO2 generated by side reactions, significantly improves defects such as bubbles, scales, and cracks that occur after the material is formed, and results in high mechanical properties and low scrap rate.

[0022] The bimetallic catalyst has the structural formula shown in formula (1):

[0023]

[0024] In the formula, R1 is a C3 alkyl group;

[0025] R2 and R3 may be the same or different, including C1-C20 alkyl, alkoxy or aralkyl-substituted alkyl;

[0026] R4 is a C2-C3 alkyl group;

[0027] n1 is 2 to 3;

[0028] n2 is 1 to 4;

[0029] m is 0 to 2

[0030] Me1 is selected from the following metal ions: Bi, Zn, Fe or Ni;

[0031] Me2 is selected from the following metal ions: Ti, Al, Mg or Li.

[0032] Preferably, in formula (1),

[0033] R1 is a C3 isoalkyl group;

[0034] R2 is -CH3, R3 is -O-C2H5;

[0035] R4 is a C3 isoalkyl group;

[0036] n1 is 2 to 3;

[0037] n2 is 1 to 4;

[0038] m is 0 to 2;

[0039] Me1 is Bi or Zn;

[0040] Me2 is: Ti, Al.

[0041] Preferably, in formula (1),

[0042] Me1 is Bi; R1 is a C3 alkyl group; R2 is -CH3 and R3 is -O-C2H5; n1 = 3; n2 is 1 to 4; Me2 is Ti; R4 is a C3 isoalkyl group; m is 0 to 1;

[0043] When n2 = 1, m = 1, and it has the following chemical structure:

[0044]

[0045] Set a in (Chemical Formula 1) as b is CH3(CH3)CH2O-; (Chemical Formula 1) is abbreviated as: (b)(Ti)(a)3(Bi);

[0046] When n2 = 2, m = 0, then (Chemical Formula 2) is abbreviated as: (Ti)(a)4(a-H)

[0050] ,

[0049] , ,

[0048] , ,

[0047] ,

[0051] ,

[0046] , 5( ,

[0045] , , , , ,

[0053] , ,

[0052] , , 2( , , , , ,

[0044] (Bi)2;

[0047] When n2 = 3, m = 0, then (Chemical Formula 3) is abbreviated as: (Ti)(a)4(a-H) 5( (Bi)3;

[0048] When n2 = 4, m = 0, then (Chemical Formula 4) is abbreviated as: (Ti)(a)4(a-H)8(Bi)4.

[0049] Alternatively, Me1 is Bi; R1 is a C3 alkyl group; R2 is -CH and R3 is -O-C2H5; n1 = 3; n, is 1 to 3; Me2 is Al; m = 0;

[0050] When n2 = 1, it has the following chemical structure:

[0051]

[0052] (Chemical Formula 5) is abbreviated as: (Al)(a)3(Bi);

[0053] When n2 = 2, then (Chemical Formula 6) is abbreviated as: (Al)(a)3(a-H)3(Bi)2;

[0054] When n2 = 3, then (Chemical Formula 7) is abbreviated as: (Al)(a)3(a-H)6(Bi)3.

[0055] Alternatively, Me1 is Zn; R1 is a C3 alkyl group; R2 is -CH3 and R3 is -O-C2H5; n1 = 2; n2 is 1 to 4; Me2 is Ti; R4 is a C3 isomeric alkyl group; m is 0 to 2.

[0056] When n2 = 1 and m = 2, it has the following chemical structure:

[0057]

[0058] (Chemical Formula 8) is abbreviated as: (b)2(Ti)(a)2(Zn);

[0059] When n2 = 2 and m = 0, then (Chemical Formula 9) is abbreviated as: (Ti)(a)4(Zn)2;

[0060] When n2 = 3 and m = 0, then (Chemical Formula 10) is abbreviated as: (Ti)(a)4(a-H)2(Zn)3;

[0061] When n2 = 4 and m = 0, then (Chemical Formula 11) is abbreviated as: (Ti)(a)4(a-H)4(Zn)4.

[0062] Alternatively, Me1 is Zn; R1 is a C3 alkyl group; R2 is -CH3 and R3 is -O-C2H5; n1 = 2; n2 is 1 to 3; Me2 is Al; R4 is a C3 isomeric alkyl group; m is 0 to 1.

[0063] Me1 is Zn; R1 is a C3 alkyl group; R2 is -CH3 and R3 is -O-C2H5; n1 = 2; n2 is 1 to 3; Me2 is Al; R4 is a C3 isomeric alkyl group; m is 0 to 1.

[0064] When n2 = 1 and m = 1, it has the following chemical structure:

[0065]

[0066] (Chemical Formula 12) is abbreviated as: (b)(Al)(a)2(Zn);

[0067] When n2 = 2 and m = 0, then (Chemical Formula 13) is abbreviated as: (Al)(a)3(a-H)(Zn)2;

[0068] When n2 = 3 and m = 0, then (Chemical Formula 14) is abbreviated as: (Al)(a)3(a-H)3(Zn)3.

[0069] Preferably, the mass ratio of the oligomeric polyol in component P1 to the chain extender in component P2 is (85-95):(5-15).

[0070] Preferably, the antioxidant and anti-yellowing agent in component P1 is UVK-CLV (produced by Guangzhou Yourun Synthetic Materials Co., Ltd.), and the amount added is 0.3-1% of the mass of component P1.

[0071] Preferably, the anti-hydrolysis agent in component P1 is CUCE-ATH (produced by Guangzhou Yourun Synthetic Materials Co., Ltd.), and the amount added is 0.3-1% of the mass of component P1.

[0072] Preferably, the antistatic agent in component P1 is CUCE-ASW (produced by Guangzhou Yourun Synthetic Materials Co., Ltd.), and the amount added is 0.5-2% of the mass of component P1.

[0073] Preferably, the chain extender in component P2 is selected from any one or a mixture of several of 1,4-butanediol, ethylene glycol, and TRP (produced by Guangzhou Yourun Synthetic Materials Co., Ltd.). More preferably, the chain extender is 1,4-butanediol.

[0074] A method for preparing the non-foaming polyurethane composition includes the following steps:

[0075] Step a. Preparation of Component I:

[0076] The oligomeric polyol and diisocyanate are mixed and reacted, and the mixture is stirred and degassed after removing water. The reaction temperature is 75-80℃ and the reaction time is 2-4 hours.

[0077] Step b. Preparation of component P1:

[0078] Mix oligomeric polyols, catalysts, antioxidants and anti-yellowing agents, anti-hydrolysis agents and antistatic agents, remove water, stir, and degas;

[0079] Step c. Preparation of polyurethane composition:

[0080] The components I, P1, and P2 are mixed in a mass ratio of I:P1:P2 = 100:(40-70):(3-8), stirred evenly, and then poured into a preheated mold for reaction and molding.

[0081] Preferably, in the preparation method of the non-foaming polyurethane composition, the oligomeric polyol and chain extender are added to a reactor equipped with a stirrer and a thermometer, stirred and heated to 105-110°C, and vacuum dehydrated for 0.5-1 h under a vacuum of -(0.095~0.1) MPa until the moisture content of the material in the reactor is less than 0.05%.

[0082] Preferably, in the method for preparing the non-foaming polyurethane composition, component I is prepared from the following components in parts by weight:

[0083] 65-70 parts of oligomeric polyols;

[0084] 30-35 parts of diisocyanate;

[0085] The P1 component is prepared from the following components in parts by weight:

[0086]

[0087] Preferably, the method for preparing the non-foaming polyurethane composition includes the following steps:

[0088] Step a. Preparation of Component I:

[0089] The weight parts of each component in the reaction system are:

[0090] 65-70 parts of oligomeric polyols;

[0091] 30-35 parts of diisocyanate;

[0092] The measured oligomeric polyol is added to a reactor equipped with a stirrer and thermometer. The mixture is stirred and heated to 105-110℃. Under a vacuum of -(0.095~0.1)MPa, water is removed by vacuum for 0.5-1h until the moisture content of the material in the reactor is below 0.05%. The temperature is then lowered to 40-50℃, the vacuum is released, and diisocyanate is slowly added while stirring. The reactor is kept sealed, and the temperature is slowly raised to 75-80℃. The reaction is maintained at this temperature for 2-3 hours. When the NCO value reaches the preset value, the mixture is vacuum defoamed, discharged, and sealed for storage to obtain component I.

[0093] Step b. Preparation of components P1 and P2:

[0094] The weight parts of each component in the reaction system are:

[0095]

[0096] The oligomeric polyol is added to a reactor equipped with a stirrer and thermometer according to the measured mass parts. The mixture is stirred and heated to 105-110℃. Under a vacuum of -(0.095~0.1)MPa, the mixture is vacuum dehydrated for 0.5-1h until the moisture content of the material in the reactor is lower than 0.05%. The temperature is then lowered to 50-60℃, and the measured mass parts of catalyst, antioxidant, anti-yellowing agent, anti-hydrolysis agent, and antistatic agent are added. The mixture is stirred evenly and then vacuum defoamed before being discharged, sealed, and stored to obtain component P1.

[0097] Preparation of the P2 component:

[0098] Add the chain extender to a reactor equipped with a stirrer and thermometer according to the measured mass fraction. Stir and heat to 100-105℃. Under vacuum of -(0.095~0.1)MPa, remove water by vacuum for 0.5-1h until the moisture content of the material in the reactor is lower than 0.05%. Cool down to 50-60℃, release the vacuum, and then discharge and seal for storage to obtain component P2.

[0099] Step c. Preparation of polyurethane composition:

[0100] The components I, P1, and P2 are mixed in a mass ratio of I:P1:P2 = 100:(40-70):(3-8), stirred evenly, and then poured into a preheated mold for reaction and molding.

[0101] An application of the aforementioned non-foaming polyurethane composition is disclosed, specifically in the manufacture of polyurethane shoe soles. The non-foaming polyurethane shoe sole is a non-foaming, highly transparent, abrasion-resistant polyurethane shoe sole.

[0102] The non-foaming polyurethane composition is used in the preparation of high-performance polyurethane casters, high-end medical device accessories, etc.

[0103] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0104] The non-foaming polyurethane composition of this invention is based on the development concept of low carbon and low energy consumption, environmental protection and safety and high product performance. It adopts the production process of medium and room temperature curing composite material semi-prepolymer method, which has significant advantages such as easy process control, flexible formulation and stable quality, low energy consumption and high efficiency.

[0105] The polyurethane shoe sole material obtained by mixing components I, P1, and P2 of the non-foaming polyurethane composition of the present invention in a preset ratio, casting in a mold, and molding at a medium temperature (80°C) has the properties of long working time, easy mold filling, fast molding and demolding, non-foaming, high transparency, high wear resistance, hydrolysis resistance, and antistatic properties.

[0106] The non-foaming polyurethane composition of the present invention is green and environmentally friendly, and does not contain restricted substances such as heavy metals, phthalates, and polycyclic aromatic hydrocarbons. The actual production process is flexible and easy to adjust, with fast molding and demolding, high production efficiency, and low scrap rate. Detailed Implementation

[0107] The embodiments of the technical solution of the present invention will be described in detail below. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and are therefore merely examples and should not be used to limit the scope of protection of the present invention. It should be noted that, unless otherwise stated, the technical or scientific terms used in this application should have the ordinary meaning understood by those skilled in the art. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field. Unless otherwise specified, the reagents and materials used in the following embodiments are commercially available.

[0108] The diisocyanate is 4,4'-diphenylmethane diisocyanate MDI100, produced by Wanhua Chemical Group Co., Ltd.; or produced by BASF, Germany; or carbodiimide-modified 4,4'-diphenylmethane diisocyanate CDMDI-100H, produced by Wanhua Chemical Group Co., Ltd.

[0109] The oligomeric polyol is poly(neopentyl adipate) diol (NPG / AA), with a hydroxyl value of 53-59 (mgKOH / g), produced by Asahikawa Chemical (Suzhou) Co., Ltd.; or polytetrahydrofuran diol (PTMG2000), with a hydroxyl value of 53-59 (mgKOH / g), produced by Mitsubishi Chemical Corporation of Japan.

[0110] The chain extender is 1,4-butanediol, manufactured by BASF in Germany; or ethylene glycol or TRP (hydroxyl value 467 mg KOH / g, functionality 3) (manufactured by Guangzhou Yourun Synthetic Materials Co., Ltd.).

[0111] The antioxidant and anti-yellowing agent is UVK-CLV, produced by Guangzhou Yourun Synthetic Materials Co., Ltd.

[0112] The anti-hydrolysis agent is CUCE-ATH, manufactured by Guangzhou Yourun Synthetic Materials Co., Ltd.

[0113] The antistatic agent is CUCE-ASW, produced by Guangzhou Yourun Synthetic Materials Co., Ltd.

[0114] The catalyst is any one or a mixture of several bimetallic catalysts with the structural formula shown in formula (1), with the substitution symbol AU:

[0115] Alternatively, the catalyst may be triethylenediamine, produced by Evonik GmbH, Germany.

[0116]

[0117] In the formula, R1 is a C3 alkyl group;

[0118] R2 and R3 may be the same or different, including C1-C20 alkyl, alkoxy or aralkyl-substituted alkyl;

[0119] R4 is a C2-C3 alkyl group;

[0120] n1 is 2 to 3;

[0121] n2 is 1 to 4;

[0122] m is 0 to 2

[0123] Me1 is selected from the following metal ions: Bi, Zn, Fe or Ni;

[0124] Me2 is selected from the following metal ions: Ti, Al, Mg or Li.

[0125] As a specific embodiment: in formula (1),

[0126] R1 is a C3 isoalkyl group;

[0127] R2 is -CH3, R3 is -O-C2H5;

[0128] R4 is a C3 isoalkyl group;

[0129] n1 is 2 to 3;

[0130] n2 is 1 to 4;

[0131] m is 0 to 2;

[0132] Me1 is either Bi or Zn;

[0133] Me2 consists of Ti and Al.

[0134] As a specific embodiment: in formula (1),

[0135] Me1 is Bi; R1 is a C3 alkyl group; R2 is -CH3 and R3 is -O-C2H5; n1 = 3; n2 is 1 to 4; Me2 is Ti; R4 is a C3 isoalkyl group; m is 0 to 1;

[0136] When n² = 1, m = 1, and it has the following chemical structure:

[0137]

[0138] In (Chemistry 1), a is set as b is CH3(CH3)CH2O-; (Chemical 1) is abbreviated as: (b)(Ti)(a)3(Bi);

[0139] When n² = 2, m = 0, then (Simplified 2) can be written as: (Ti)(a)⁴(aH) 2( Bi)2;

[0140] When n² = 3, m = 0, then (3) can be simplified to: (Ti)(a)⁴(aH) 5( Bi)3;

[0141] When n2 = 4, m = 0, then (Chemical Formula 4) is abbreviated as: (Ti)(a)4(a-H)8(Bi)4.

[0142] Alternatively, Me1 is Bi; R1 is a C3 alkyl group; R2 is -CH3 and R3 is -O-C2H5; n1 = 3; n2 is 1 to 3; Me2 is Al; m = 0;

[0143] When n2 = 1, it has the following chemical structure:

[0144]

[0145] (Chemical Formula 5) is abbreviated as: (Al)(a)3(Bi);

[0146] When n2 = 2, then (Chemical Formula 6) is abbreviated as: (Al)(a)3(a-H)3(Bi)2;

[0147] When n2 = 3, then (Chemical Formula 7) is abbreviated as: (Al)(a)3(a-H)6(Bi)3.

[0148] Alternatively, Me1 is Zn; R1 is a C3 alkyl group; R2 is -CH3 and R3 is -O-C2H5; n1 = 2; n2 is 1 to 4; Me2 is Ti; R4 is a C3 isoalkyl group; m is 0 to 2.

[0149] When n2 = 1 and m = 2, it has the following chemical structure:

[0150]

[0151] (Chemical Formula 8) is abbreviated as: (b)2(Ti)(a)2(Zn);

[0152] When n2 = 2 and m = 0, then (Chemical Formula 9) is abbreviated as: (Ti)(a)4(Zn)2;

[0153] When n2 = 3 and m = 0, then (Chemical Formula 10) is abbreviated as: (Ti)(a)4(a-H)2(Zn)3;

[0154] When n2 = 4 and m = 0, then (Chemical Formula 11) is abbreviated as: (Ti)(a)4(a-H)4(Zn)4.

[0155] Alternatively, Me1 is Zn; R1 is a C3 alkyl group; R2 is -CH3 and R3 is -O-C2H5; n1 = 2; n2 is 1 to 3; Me2 is Al; R4 is a C3 isoalkyl group; m is 0 to 1.

[0156] When n2 = 1 and m = 1, it has the following chemical structure:

[0157]

[0158] (Chemical formula 12) is abbreviated as: (b)(Al)(a)2(Zn);

[0159] When n2 = 2 and m = 0, then (Chemical formula 13) is abbreviated as: (Al)(a)3(a-H)(Zn)2;

[0160] When n2 = 3 and m = 0, then (Chemical formula 14) is abbreviated as: (Al)(a)3(a-H)3(Zn)3.

[0161] Examples 1 to 3 and Comparative Examples 1 to 3

[0162] A preparation method of a non-foaming polyurethane composition, comprising the following steps:

[0163] Step a. Preparation method of Component I

[0164] Add 69 g of neopentyl glycol adipate diol into a reactor equipped with a stirrer and a thermometer, stir and heat up to 105 - 110 °C, under a vacuum of -(0.095 - 0.1) MPa, vacuum dehydrate for 0.5 - 1 h until the moisture content of the material in the reactor is lower than 0.05%, cool down to 40 - 50 °C, relieve the vacuum, and slowly add 31 g of 4,4'-diphenylmethane diisocyanate under stirring. Keep the reaction kettle sealed, slowly heat up to 75 - 80 °C, hold the reaction for 2 - 3 hours, take a sample to measure the NCO value to reach the preset 7.5%, then vacuum defoam, discharge the material and seal it for storage to obtain Component I.

[0165] Step b. Preparation method of Component P1

[0166] Add the measured mass parts of neopentyl glycol adipate diol and polytetrahydrofuran diol into a reactor equipped with a stirrer and a thermometer according to Table 1, stir and heat up to 105 - 110 °C, under a vacuum of -(0.095 - 0.1) MPa, vacuum dehydrate for 0.5 - 1 h until the moisture content of the material in the reactor is lower than 0.05%, cool down to 50 - 60 °C, relieve the vacuum, add 0.2 g of catalyst, 0.3 g of antioxidant and anti-yellowing agent UVK-CLV, 0.5 g of anti-hydrolysis agent CUCE-ATH, 0.5 g of antistatic agent CUCE-ASW, mix and stir evenly, and then discharge and seal it for storage after vacuum defoaming to obtain Component P1.

[0167] Among them, in Examples 1 to 3 of the present invention, catalyst AU is used, and in Comparative Examples 1 to 3, a triethylenediamine solution is used as the catalyst.

[0168] The preparation method of the triethylenediamine solution is as follows: 33g of solid triethylenediamine is added to 67g of 1,4-butanediol, heated to 80°C under sealed conditions, and stirred continuously until the solid triethylenediamine is completely dissolved and becomes a transparent and clear solution. The solution is then cooled, sealed, and stored.

[0169] Preparation method of component P2:

[0170] 1,4-Butanediol was added to a reactor equipped with a stirrer and a thermometer. The mixture was stirred and heated to 100-105°C. Under a vacuum of -0.095 to 0.1 MPa, the material was dehydrated for 0.5-1 hours until the moisture content of the material in the reactor was below 0.05%. The temperature was then lowered to 50-60°C. After the vacuum was released, the material was discharged, sealed, and stored to obtain component P2.

[0171] Step c. Preparation method of mixed reactants

[0172] Take appropriate amounts of the independent components I, P1, and P2 prepared according to the above method, place them in the independent material tanks of the three-component casting machine, preheat them to 60°C while keeping them sealed, and then mix them according to the mass ratio set in Table 1 and pour them into a suitable mold that has been preheated to 80°C. Keep the temperature at 80°C for further reaction and molding.

[0173] Examples 4-6

[0174] A method for preparing a non-foaming polyurethane composition includes the following steps:

[0175] Preparation method of component aI in step a

[0176] Add poly(neopentyl adipate) glycol diol to a reactor equipped with a stirrer and thermometer according to Table 1. Stir and heat to 105-110℃. Under vacuum of -0.095-0.1 MPa, dehydrate under vacuum for 0.5-1h until the moisture content of the material in the reactor is below 0.05%. Cool down to 40-50℃, release the vacuum, and slowly add diisocyanate while stirring. Keep the reactor sealed and slowly heat to 75-80℃. Maintain the temperature for 2-3 hours. Take a sample to measure the NCO value. Once it reaches the preset value, defoam under vacuum, discharge the material, and seal it for storage to obtain component I.

[0177] Step b. Preparation method of component P1

[0178] According to Table 1, the measured mass parts of poly(neopentyl adipate) glycol and polytetrahydrofuran glycol are added to a reactor equipped with a stirrer and a thermometer. The mixture is stirred and heated to 105-110℃. Under a vacuum of -(0.095~0.1)MPa, the mixture is vacuum dehydrated for 0.5-1h until the moisture content of the material in the reactor is lower than 0.05%. The temperature is then lowered to 50-60℃, and the vacuum is released.

[0179] Add catalyst AU, antioxidant and anti-yellowing agent UVK-CLV, anti-hydrolysis agent CUCE-ATH, and antistatic agent CUCE-ASW according to the mass proportions measured in Table 1, mix and stir evenly, remove bubbles under vacuum, and then discharge and seal for storage to obtain component P1.

[0180] Preparation method of component P2:

[0181] Add the chain extender to a reactor equipped with a stirrer and thermometer according to Table 1, stir and heat to 100-105℃, and remove water under vacuum of -(0.095~0.1)MPa for 0.5-1h until the moisture content of the material in the reactor is lower than 0.05%. Cool down to 50-60℃, release the vacuum, and then discharge and seal for storage to obtain component P2.

[0182] Step c. Preparation method of mixed reactants

[0183] Take appropriate amounts of the independent components I, P1, and P2 prepared according to the above method, place them in the independent material tanks of the three-component casting machine, preheat them to 60°C while keeping them sealed, and then mix them according to the mass ratio set in Table 2 and pour them into a suitable mold that has been preheated to 80°C. Keep the temperature at 80°C for further reaction and molding.

[0184] Table 1 shows the raw material combinations and numbers of the examples and comparative examples of mixing and reacting to form the product according to the above method.

[0185] Material testing methods

[0186] Table 2 shows a comparison of the gel time, molding time, appearance, and performance of the polyurethane compositions of the examples and comparative examples prepared according to the above method. Shore hardness was tested according to GB / T 531.1-2008; tensile properties were tested according to GB / T 528-2009; tear strength was tested according to GB / T 529-2008; and abrasion resistance was tested according to GB / T 9867-2008.

[0187] Table 1. Raw material combinations and numbering for examples and comparative examples of mixed reaction molding.

[0188]

[0189] Table 2. Curing process and post-curing appearance and performance analysis of polyurethane compositions.

[0190]

[0191] As can be seen from Table 2, the material molding properties of Examples 1-6 and Comparative Examples 1-3 of the present invention all meet the requirements of the HG / T 3082-2010 rubber shoe sole standard, and have the properties of long operation time, easy mold filling, fast molding and demolding, non-foaming, high transparency, high wear resistance, hydrolysis resistance and antistatic properties.

[0192] Compared with Comparative Examples 1-3, it is evident that the materials using catalyst AU in Examples 1-3 exhibit significantly better appearance and molding performance than those using triethylenediamine solution. Because catalyst AU has the characteristic of targeted catalysis of isocyanate and hydroxyl reactions, and is insensitive to trace amounts of moisture in the material, it avoids the CO2 generated by side reactions, significantly improving defects such as bubbles and pinholes after material molding. This results in high material mechanical properties and a low scrap rate. Using catalyst AU is the optimal implementation method of this invention. The above embodiments are only used to illustrate the technical solutions of this invention and are not intended to limit it. Although the invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this invention, and they should all be covered within the scope of the claims and specification of this invention.

Claims

1. A non-foaming polyurethane composition, characterized in that, It is prepared from the following components: Component I is an -NCO-terminated prepolymer oligomer obtained by prepolymerization of diisocyanate and oligomeric polyol; Component P1 includes oligomeric polyols, catalysts, antioxidants and anti-yellowing agents, anti-hydrolysis agents, and antistatic agents; Component P2 is a chain extender; The mass ratio of component I, component P1, and component P2 is I:P1:P2 = 100:(40-70):(3-8); The diisocyanate in component I is 4,4'-diphenylmethane diisocyanate or carbodiimide-modified 4,4'-diphenylmethane diisocyanate. The catalyst in component P1 is a bimetallic catalyst, with the structural formulas shown in (1), (5), (8), and (12): (Chemistry 1) (Chemistry 5) (Chemistry 8) (Chemistry 12).

2. The non-foaming polyurethane composition according to claim 1, characterized in that, The oligomer polyol in component I is a polyester polyol with a hydroxyl value of 53-59 (mgKOH / g).

3. The non-foaming polyurethane composition according to claim 2, characterized in that, The mass ratio of diisocyanate to polyester polyol in component I is (30-35):(65-70), and the NCO value is 7-8.

4. The non-foaming polyurethane composition according to claim 1, characterized in that, The oligomer polyol in component P1 is selected from any one or a mixture of two of polyester polyols or polyether polyols.

5. The non-foaming polyurethane composition according to claim 4, characterized in that, The polyester polyol in component P1 is poly(neopentyl adipate) diol with a hydroxyl value of 53-59 (mgKOH / g); the polyether polyol is polytetrahydrofuran diol with a hydroxyl value of 53-59 (mgKOH / g).

6. The non-foaming polyurethane composition according to claim 1, characterized in that, The catalyst in component P1 is a bimetallic catalyst, and the amount added is 0.1-0.5% of the mass of component P1.

7. The non-foaming polyurethane composition according to claim 1, characterized in that, The mass ratio of the oligomeric polyol in component P1 to the chain extender in component P2 is (85-95):(5-15).

8. A method for preparing the non-foaming polyurethane composition according to any one of claims 1 to 7, characterized in that, Includes the following steps: Step a. Preparation of Component I: The oligomeric polyol and diisocyanate are mixed and reacted, and the mixture is stirred and degassed after removing water. The reaction temperature is 75-80℃ and the reaction time is 2-4 hours. Step b. Preparation of component P1: Mix oligomeric polyols, catalysts, antioxidants and anti-yellowing agents, anti-hydrolysis agents and antistatic agents, remove water, stir, and degas; Step c. Preparation of polyurethane composition: Mix the components I, P1, and P2 in a mass ratio of I:P1:P2 = 100:(40-70):(3-8), stir evenly, and then pour into a preheated mold to react and form.

9. The application of the non-foaming polyurethane composition according to any one of claims 1 to 7, characterized in that, It is used in the manufacture of polyurethane shoe soles, high-performance polyurethane casters, and high-end medical device accessories.

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