A kind of anti-skid polyurethane sole resin and preparation method thereof

Abstract

The invention discloses a non-slip polyurethane sole resin and a preparation method thereof, comprising component A and component B; component A comprises: 50 to 70 parts of polyester polyol A1, 10 to 30 parts of hydroxyl-terminated poly 1,2-butadiene A2; component B comprises: 50 to 70 parts of isocyanate B1, 20 to 45 parts of hydroxyl-terminated poly 1,2-butadiene B2 and 1 to 10 parts of polyether polyol B3; wherein polyester polyol A1 is prepared by esterification reaction of 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol and 1,2-propylene glycol with adipic acid. The resin of the invention has good gripping ability, excellent non-slip property, and the prepared polyurethane sole has large friction and excellent anti-slip performance.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane, and in particular relates to an anti-slip polyurethane sole resin and a preparation method thereof. Background Art

[0002] Polyurethane materials have excellent performance, and their strength and hardness are adjustable, and their application fields are very wide. Polyurethane is a polymer with repeating structural units of carbamate segments made by the reaction of isocyanate and polyol. It consists of soft segments and hard segments. The soft segments are composed of polyols such as long-chain polyester polyols and polyether polyols, and the hard segments are obtained by the reaction of isocyanate groups with small molecule polyols or small molecule polyamines.

[0003] Compared with ordinary rubber soles, polyurethane soles have the characteristics of light weight and good wear resistance. Polyurethane soles use polyurethane stock solution as the main raw material. By adding various additives, polyurethane soles with different hardness, density, wear resistance, oil resistance, electrical insulation, antistatic and acid and alkali resistance can be prepared. However, due to the molecular structure characteristics of polyurethane, the anti-slip performance of using it to make medium-hardness soles is not enough, and it is easy to make people slip when walking on some relatively slippery surfaces. The anti-slip property of the sole directly affects the comfort and safety of the shoes when they are worn.

[0004] In view of the above problems, many researchers are currently working on optimizing the formula of polyurethane materials and improving the anti-slip performance of polyurethane. For example: Patent document CN 108285524A discloses an anti-slip polyurethane elastomer stock solution and its preparation method and application, comprising polyurethane stock solution component A and polyurethane stock solution component B; polyurethane stock solution component A contains polyether ester diol and polyester polyol, and the anti-slip agent contains rosin, liquid rubber, zinc oxide and plasticizer; polyurethane stock solution component B contains terminal hydroxyl liquid rubber modified polyester polyol; its anti-slip principle is to provide higher friction through natural rosin and / or rosin resin in the anti-slip agent. Patent document CN 111234510 A discloses a polyurethane resin and its preparation method and application, which can be used for decorative materials with anti-slip requirements in the synthetic leather industry. In this document, by adding rosin ester diol in the final stage of polyurethane synthesis and connecting it to the structure of polyurethane resin, the anti-slip property of polyurethane resin is improved. However, most of the above literature on improving the anti-slip performance is to add rosin resin to polyurethane resin; however, the color of rosin resin is relatively dark, which can easily color the polyurethane resin and cause the hydrolysis resistance of the polyurethane resin to decrease, thus limiting its scope of use.

[0005] The invention designs the polyurethane molecular structure, synthesizes polyols with special structures and selects suitable raw materials to synthesize polyurethane resin with excellent anti-slip effect. Summary of the invention

[0006] In view of the deficiencies in the prior art, the object of the present invention is to provide a non-slip polyurethane sole resin and a preparation method thereof, which has the characteristics of good physical and mechanical properties, high friction coefficient and excellent non-slip performance.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] The present invention provides a non-slip polyurethane sole resin, comprising component A and component B;

[0009] The component A comprises the following raw materials in parts by weight: 50 to 70 parts of polyester polyol A1, 10 to 30 parts of hydroxyl-terminated poly 1,2-butadiene A2; the total parts of the component A is 100 parts;

[0010] The B component includes the following raw materials in parts by weight: 50 to 70 parts of isocyanate B1, 20 to 45 parts of terminal hydroxyl poly 1,2-butadiene B2 and 1 to 10 parts of polyether polyol B3; the total parts of the B component is 100 parts;

[0011] The polyester polyol A1 is prepared by esterification reaction of 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol and 1,2-propylene glycol with adipic acid; its number average molecular weight is 2000-3000, such as 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900 or 3000; preferably, the mass percentage of raw materials in the polyester polyol A1 is: 2-ethyl-1,3-hexanediol 3%-18%, 3-methyl-1,5-pentanediol 3%-15%, 1,2-propylene glycol 3%-20%, adipic acid 47%-70%;

[0012] The terminal hydroxyl poly 1,2-butadiene A2 is a polybutadiene with a number average molecular weight of 1800 to 2200, a functionality of 1.9 to 2.2, and a 1,2-ethyl content of ≥85%. Different from linear terminal hydroxyl poly 1,4-butadiene, the branched terminal hydroxyl poly 1,2-butadiene A2 has a high content of 1,2-ethyl branching groups, which can greatly increase the probability of polymer molecules contacting the ground at the microscopic level, providing excellent gripping ability;

[0013] The isocyanate B1 is at least one of 4,4-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate and / or naphthalene diisocyanate;

[0014] The terminal hydroxyl poly 1,2-butadiene B2 is a polybutadiene with a number average molecular weight of 2600 to 3200, a functionality of 1.9 to 2.2, and a 1,2-ethyl content of ≥85%; the terminal hydroxyl poly 1,2-butadiene B2 has a large number of molecular chain branching groups, a relatively long flexible molecular chain structure, and an outstanding anti-slip effect, and can give the B component excellent anti-slip properties, greatly improving the friction coefficient of the product;

[0015] The polyether polyol B3 is a polyethylene oxide-propylene oxide polyol having a functionality of 2.8 to 3 and a number average molecular weight of 3000 to 6000, such as 3100, 3300, 3500, 4000, 4500, 5000 or 5500.

[0016] Preferably, the raw materials for preparing the A component also include 5 to 10 parts of a chain extender.

[0017] Preferably, the chain extender is any one of ethylene glycol, 1,4-butanediol, 1,3-propylene glycol, or a combination of at least two thereof.

[0018] Preferably, the raw materials for preparing component A also include 0.1 to 2 parts of a cross-linking agent.

[0019] Preferably, the cross-linking agent is any one of glycerol, trimethylolpropane or 1,2,6-hexanetriol, or a combination of at least two thereof.

[0020] Preferably, the raw materials for preparing component A also include 0.2 to 3 parts of a foaming agent.

[0021] Preferably, the blowing agent is water.

[0022] Preferably, the raw materials for preparing component A also include 0.3 to 0.9 parts of a surfactant.

[0023] Preferably, the surfactant is an organosilicon foam stabilizer.

[0024] Preferably, the raw materials for preparing the A component also include 0.7 to 3 parts of a catalyst.

[0025] Preferably, the catalyst of component A is a mixture of triethylenediamine and ethylene glycol in a mass ratio of 1:2 to 1:3 (for example, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 or 1:3, etc.); further preferably, the mass ratio of triethylenediamine to ethylene glycol solution is 1:2 to 1:2.3.

[0026] Preferably, the component A is composed of the following components in parts by weight: polyester polyol A1: 50-70 parts, terminal hydroxyl poly 1,2-butadiene A2: 10-30 parts, chain extender: 5-8 parts, cross-linking agent: 0.5-1.8 parts, foaming agent: 0.2-1.5 parts, surfactant: 0.4-0.6 parts, catalyst: 0.7-3 parts.

[0027] Preferably, the raw materials for preparing the B component further include a side reaction inhibitor accounting for 0.001% to 0.008% of the total mass of the B component.

[0028] Preferably, the side reaction inhibitor is phosphoric acid and / or benzoyl chloride.

[0029] The method for preparing the anti-slip polyurethane resin for shoe soles of the present invention comprises the following steps: (1) mixing the raw materials for preparing component A at 50-60° C. for 1.5-2.5 hours, and cooling to 40-45° C. to obtain the component A; and (2) mixing the raw materials for preparing component B evenly, reacting at a temperature of 60-70° C. for 2-3 hours, and obtaining component B.

[0030] The application of the anti-slip polyurethane sole resin of the present invention is used to prepare polyurethane soles; the preparation method of the polyurethane sole comprises the following steps: mixing component A and component B, injecting into a mold for reaction molding, demoulding, and aging to obtain the polyurethane sole; the ratio of the total molar number of active hydrogen in the raw material for preparing component A to the total molar number of isocyanate groups in the raw material for preparing component B is 1:(0.99-1.03).

[0031] Preferably, the temperature of component A and component B is maintained at 40-45°C before mixing, the reaction temperature in the mold is 45-55°C, and the reaction time is 3-5 minutes; the aging temperature is 55-70°C, and the aging time is 6-24 hours.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention uses polyester polyol A1, terminal hydroxyl poly 1,2-butadiene, isocyanate B1 and polyether polyol B3 in combination to form a chemically cross-linked network structure, so that the anti-skid polyurethane sole resin has excellent tensile strength, tear strength and other mechanical properties; the soft and hard segments in the molecular structure are reasonably matched, the soft and hard segments have good phase separation, the soft segment molecular chain has a reasonable branching structure and different molecular chain lengths, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol and 1,2-propylene glycol in the raw materials of polyester polyol A1 are all branched, especially 2-ethyl-1,3-hexanediol contains a longer ethyl branching group, the branched molecular chain segment can be better anchored on the ground, has a good adsorption effect, the anti-skid polyurethane sole resin has good grip ability, excellent anti-skid property, the prepared polyurethane sole has large friction force, excellent anti-skid property, and greatly improves walking safety. DETAILED DESCRIPTION

[0034] Those skilled in the art should recognize that the present embodiment is only used to illustrate the present invention, and is not used to limit the present invention. Any changes or modifications to the embodiment within the scope of the present invention are within the scope of the claims of the present invention.

[0035] The raw materials used in the following examples and comparative examples of the present invention are as follows:

[0036] Polyester polyol A1 was prepared by the following method:

[0037] With stirring turned on, 17.0 g of 2-ethyl-1,3-hexanediol, 14.0 g of 3-methyl-1,5-pentanediol, 13.0 g of 1,2-propylene glycol and 56.0 g of adipic acid were added in sequence to a reactor equipped with nitrogen, condensation reflux and vacuum devices; after the feeding was completed, the temperature was raised to 140°C and stirred for dehydration reaction for 3 hours, and then the temperature was raised to 200°C and stirred for reaction for 5 hours, 0.01 g of catalyst tetraisopropyl titanate was added, and the reaction was carried out for 4 hours at a vacuum degree of less than -0.098 MPa, and then sampling and detection were performed to obtain polyester polyol A1 with an acid value of 0.5 mgKOH / g and a hydroxyl value of 56.1 mgKOH / g. The acid value of the polyester polyol was measured according to standard HG / T 2708-1995, and the hydroxyl value of the polyester polyol was measured according to standard HG / T 2709-1995. The number average molecular weight = 112200 / hydroxyl value. The number average molecular weight of the polyester polyol A1 was calculated to be 2000.

[0038] Catalyst: a mixture of triethylenediamine and ethylene glycol in a mass ratio of 1:2.

[0039] Surfactant: DC-193, American Gas Company.

[0040] Hydroxyl-terminated polybutadiene 1,2 A2: G-2000, Nippon Soda Co., Ltd.

[0041] Hydroxyl-terminated polybutadiene B2: G-3000, Nippon Soda Co., Ltd.

[0042] Polyether polyol B3: C-3156, Yantai Wanhua Chemical Co., Ltd.

[0043] Example 1

[0044] The anti-slip polyurethane shoe sole resins of Examples 1 to 7 and Comparative Examples 1 to 7 include component A and component B, and are prepared as follows:

[0045] Preparation of component A: polyester polyol A1, terminal hydroxyl poly 1,2-butadiene A2 (G-2000), ethylene glycol, propylene glycol, catalyst, water and surfactant DC-193 were mixed and stirred at 55° C. for 2 hours, then cooled to 40° C. and mixed for 1 hour to obtain the component A.

[0046] Preparation of component B: Isocyanate B1 (4,4-diphenylmethane diisocyanate), terminal hydroxyl liquid rubber B2 (G-3000), polyether polyol B3 (C-3156) and phosphoric acid were mixed and reacted at 65° C. for 2 hours to obtain component B.

[0047] The formulas of Examples 2 to 7 and Comparative Examples 1 to 7 are specifically shown in Tables 1 and 2, and the preparation method is the same as that of Example 1. Among them, the polyester polyol A3 of Comparative Examples 1 to 7 is a polyester polyol with a number average molecular weight of 2000 obtained by esterification reaction of ethylene glycol, diethylene glycol and adipic acid, produced by Asahikawa Chemical (Suzhou) Co., Ltd., with a brand name of XCPP-21017; the polyester polyol B4 is a polyester polyol with a number average molecular weight of 2000 obtained by esterification reaction of ethylene glycol, 1,4-butanediol and adipic acid, produced by Asahikawa Chemical (Suzhou) Co., Ltd., with a brand name of XCPP-20013.

[0048] Table 1 Weight ratio of raw materials in Examples 1 to 7, unit: weight parts

[0049]

[0050] Table 2 Weight ratio of raw materials in comparative examples 1 to 7, unit: weight parts

[0051]

[0052] The anti-skid polyurethane sole resin of Examples 1 to 7 and Comparative Examples 1 to 7 is used to prepare a polyurethane sole. The preparation method is as follows: Component A at a temperature of 40°C and Component B at a temperature of 40°C are mixed in a casting machine, the contents of Component A and Component B are controlled so that the ratio of the total number of active hydrogen moles in the raw material of Component A to the total number of isocyanate group moles in the raw material of Component B is 1:1, and the mixture is injected into a mold at 45°C for reaction for 5 minutes, demoulded, and aged in an oven at 60°C for 8 hours to obtain a polyurethane sole. The performance test results of the anti-skid polyurethane sole resin and the polyurethane sole of Examples 1 to 7 and Comparative Examples 1 to 7 are listed in Tables 3 and 4.

[0053] Table 3 Test results of Examples 1 to 7

[0054] Test items Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 <![CDATA[Density (g / cm 3 )]]> 0.65 0.65 0.51 0.50 0.65 0.65 0.65 Hardness (Shore A) 61 60 55 53 61 62 60 Tensile strength (Mpa) 12.2 12.5 11.0 11.5 12.8 11.8 13.3 Elongation at break (%) 545 530 480 510 560 530 560 Tear strength (N / mm) 16.2 16.0 15.5 17.2 15.8 16.3 15.5 Dry anti-slip 0.85 0.90 0.95 0.90 0.95 0.85 0.86 Wet non-slip 0.63 0.64 0.70 0.75 0.75 0.60 0.61

[0055] Table 4 Test results of comparative examples 1 to 7

[0056] Test items Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 <![CDATA[Density (g / cm 3 ).]]> 0.65 0.52 0.51 0.65 0.65 0.65 0.65 Hardness (Shore A) 62 59 54 58 63 40 63 Tensile strength (Mpa) 14.5 15.0 12.8 8.9 12.4 7.9 15.5 Elongation at break (%) 510 350 370 700 470 790 410 Tear strength (N / mm) 19.0 21.6 18.5 10.8 17.3 8.5 22.0 Dry anti-slip 0.75 0.70 0.72 0.90 0.65 0.95 0.40 Wet non-slip 0.45 0.40 0.45 0.45 0.35 0.45 0.20

[0057] It can be seen from Tables 3 and 4 that the polyurethane soles prepared by using the anti-slip polyurethane sole resins of Examples 1 to 7 have a molding density of 0.5 to 0.65 g / cm 3 The tensile strength is 11.0-12.8Mpa, the tear strength is 15.5-17.2N / mm, the dry anti-slip coefficient is 0.80-0.95, and the wet anti-slip coefficient is 0.60-0.75. It has good physical and mechanical properties and excellent anti-slip performance.

[0058] Compared with Example 2, if the content of polyester polyol A1 in component A is too low and the content of polyester polyol A3 is too high (Comparative Example 1), the tensile strength and tear strength of the prepared polyurethane sole are slightly improved, but the dry anti-slip coefficient and the wet anti-slip coefficient both decrease to a certain extent, and the anti-slip performance is reduced.

[0059] Compared with Example 3, if the content of polyester polyol A1 in component A is too high (Comparative Example 2), the hardness, tensile strength and tear strength of the obtained polyurethane sole are greatly improved, but the elongation at break is greatly reduced, the dry anti-slip coefficient and the wet anti-slip coefficient are both reduced to a certain extent, and the anti-slip performance is reduced.

[0060] Compared with Example 4, if the content of terminal hydroxyl poly 1,2-butadiene A2 in component A is too low and the content of polyester polyol A3 is too high (Comparative Example 3), the tensile strength and tear strength of the prepared polyurethane sole are slightly improved, but the dry anti-slip coefficient and wet anti-slip coefficient both decrease to a certain extent, and the anti-slip performance is reduced.

[0061] Compared with Example 5, if the content of terminal hydroxyl poly 1,2-butadiene A2 in component A is too high (Comparative Example 4), the hardness, tensile strength and tear strength of the obtained polyurethane sole decrease significantly, but the elongation at break is greatly improved, and the dry anti-slip coefficient and wet anti-slip coefficient are both relatively high, with good anti-slip performance.

[0062] Compared with Example 6, if the content of terminal hydroxyl poly 1,2-butadiene B2 in component B is too low and the content of polyester polyol B4 is too high (Comparative Example 5), the tensile strength and tear strength of the prepared polyurethane sole are slightly improved, but the dry anti-slip coefficient and wet anti-slip coefficient both decrease to a certain extent, and the anti-slip performance is reduced.

[0063] Compared with Example 7, if the content of terminal hydroxyl poly-1,2-butadiene B2 in component B is too high (Comparative Example 6), the hardness, tensile strength and tear strength of the obtained polyurethane sole decrease significantly, but the elongation at break is greatly improved, and the dry anti-slip coefficient and wet anti-slip coefficient are both relatively high, with good anti-slip performance.

[0064] Compared with Example 7, if the contents of polyester polyol A1 and terminal hydroxyl poly 1,2-butadiene A2 in component A are too low and the content of polyester polyol A3 is too high, and at the same time the content of terminal hydroxyl poly 1,2-butadiene B2 in component B is too low and the content of polyester polyol B4 is too high (Comparative Example 7), the hardness, tensile strength and tear strength of the prepared polyurethane sole are all improved to a certain extent, and the elongation at break is slightly decreased, but the dry anti-slip coefficient and the wet anti-slip coefficient are greatly decreased, and the anti-slip performance is poor.

[0065] It can be seen that in the present invention, by controlling the content of each component within a specific range, the polyurethane resin for shoe soles prepared has excellent anti-slip properties while taking into account certain physical and mechanical properties.

Claims

1. A non-slip polyurethane sole resin, characterized in that: It includes component A and component B; The component A comprises the following raw materials in parts by weight: 50-70 parts of polyester polyol A1, 10-30 parts of hydroxy-terminated poly 1,2-butadiene A2 and 5-10 parts of chain extender, and also comprises one or more of 0.1-2 parts of cross-linking agent, 0.2-3 parts of foaming agent, 0.3-0.9 parts of surfactant and / or 0.7-3 parts of catalyst; The B component includes the following raw materials in parts by weight: 50 to 70 parts of isocyanate B1, 20 to 45 parts of hydroxyl-terminated poly 1,2-butadiene B2 and 1 to 10 parts of polyether polyol B3; and also includes a side reaction inhibitor accounting for 0.001% to 0.008% of the total weight of the B component; The polyester polyol A1 is prepared by esterification reaction of 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol and 1,2-propylene glycol with adipic acid; its number average molecular weight is 2000-3000; the mass percentage of raw materials in the polyester polyol A1 is: 2-ethyl-1,3-hexanediol 3%-18%, 3-methyl-1,5-pentanediol 3%-15%, 1,2-propylene glycol 3%-20%, adipic acid 47%-70%; The hydroxy-terminated poly 1,2-butadiene A2 is a polybutadiene having a number average molecular weight of 1800 to 2200, a functionality of 1.9 to 2.2, and a 1,2-ethyl content of ≥85%; The isocyanate B1 is at least one of 4,4-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate and / or naphthalene diisocyanate; The hydroxy-terminated poly 1,2-butadiene B2 is a polybutadiene having a number average molecular weight of 2600 to 3200, a functionality of 1.9 to 2.2, and a 1,2-ethyl content of ≥85%; The polyether polyol B3 is a polyethylene oxide-propylene oxide polyol with a functionality of 2.8 to 3 and a number average molecular weight of 3000 to 6000.

2. The anti-slip polyurethane shoe sole resin according to claim 1, characterized in that: The chain extender is any one of ethylene glycol, 1,4-butanediol, and 1,3-propylene glycol, or a combination of at least two of them.

3. The anti-slip polyurethane shoe sole resin according to claim 1, characterized in that: The cross-linking agent is any one of propylene glycol, trimethylolpropane or 1,2,6-hexanetriol or a combination of at least two thereof; the foaming agent is water; the surfactant is an organic silicon foaming agent; and the catalyst is a mixture of triethylenediamine and ethylene glycol in a mass ratio of 1:2 to 1:

3.

4. The anti-slip polyurethane shoe sole resin according to claim 1, characterized in that: The A component is composed of the following components in parts by weight: Composition: polyester polyol A1: 50-70 parts, terminal hydroxyl poly 1,2-butadiene A2: 10-30 parts, chain extender: 5-8 parts, cross-linking agent: 0.5-1.8 parts, foaming agent: 0.2-1.5 parts, surfactant: 0.4-0.6 parts, catalyst: 0.7-3 parts.

5. The anti-slip polyurethane shoe sole resin according to claim 1, characterized in that: The side reaction inhibitor is phosphoric acid and / or benzoyl chloride.

6. The method for preparing the anti-slip polyurethane shoe sole resin according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: (1) stirring the raw materials for preparing component A at 50-60° C. for 1.5-2.5 hours, and cooling the mixture to 40-45° C. to obtain component A; and (2) mixing the raw materials for preparing component B uniformly, reacting the mixture at 60-70° C. for 2-3 hours to obtain component B.

7. The use of the anti-slip polyurethane shoe sole resin according to any one of claims 1 to 5, characterized in that: Used to prepare polyurethane soles; the preparation method of the polyurethane sole comprises the following steps: mixing component A and component B, injecting into a mold for reaction molding, demoulding, and aging to obtain the polyurethane sole; the ratio of the total number of moles of active hydrogen in the raw material for preparing component A to the total number of moles of isocyanate groups in the raw material for preparing component B is 1:(0.99-1.03).

8. The use of the anti-slip polyurethane shoe sole resin according to claim 7, characterized in that: The temperature of the components A and B is maintained at 40-45° C. before mixing, the reaction temperature in the mold is 45-55° C., and the reaction time is 3-5 minutes; the aging temperature is 55-70° C., and the aging time is 6-24 hours.

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