阅读说明：本技术 一种鞋用聚氨酯组合物的制备方法及其成型体 (Preparation method of polyurethane composition for shoes and formed body thereof ) 是由 章芬成 赵叶宝 蔡万东 章海飞 池雨 于 2020-07-21 设计创作，主要内容包括：本发明是一种鞋用聚氨酯组合物的制备方法及其成型体,该鞋用聚氨酯组合物包括分离的A组分、B组分和C组分,该聚氨酯成型体通过A、B、C三种组分混合后发泡成型制得：将A组分和C组分在40～60℃下按照重量份100:1～100:3比例混合均匀得到A、C组分混合物组分,控制混合物组分中活泼氢的摩尔数与B组分的-NCO摩尔数之比为1：1,在双组份浇注机中混合后,注入40～60℃的模具中反应2～5min成型,脱模后在60～70℃烘箱中后熟化24h,即得所述的聚氨酯成型体。该产品制备的聚氨酯成型体可用于制备劳保鞋及安全鞋的鞋底部件,具有优良的防静电性能,明显提高了其的抗拉强度、撕裂强度等力学性能和耐磨等。(The invention relates to a preparation method of a polyurethane composition for shoes and a formed body thereof, the polyurethane composition for shoes comprises a component A, a component B and a component C which are separated, and the polyurethane formed body is prepared by mixing A, B, C three components and then foaming and forming: uniformly mixing the component A and the component C at 40-60 ℃ according to the weight ratio of 100: 1-100: 3 to obtain A, C component mixture component, wherein the ratio of the mole number of active hydrogen in the mixture component to the mole number of-NCO in the component B is controlled to be 1: 1, mixing in a two-component casting machine, injecting into a mold at 40-60 ℃ for reaction for 2-5 min for molding, demolding, and post-curing in an oven at 60-70 ℃ for 24h to obtain the polyurethane molded body. The polyurethane formed body prepared by the product can be used for preparing sole parts of safety shoes and safety shoes, has excellent antistatic performance, and obviously improves the mechanical properties such as tensile strength, tearing strength and the like, wear resistance and the like.)

1. A preparation method of a polyurethane composition for shoes is characterized in that the polyurethane composition for shoes comprises an A component, a B component and a C component which are separated, and the preparation method comprises the following steps:

preparing a component A:

in parts by weight, 100 parts by weight of polyester polyol A and 3-10 parts by weight of chain extender are fully mixed for 2-4 hours at 30-50 ℃ in the presence of 0.1-1 part by weight of water, and then cooled to normal temperature to obtain a component A;

preparing a component B:

placing 40-80 parts by weight of polyisocyanate in a nitrogen-protected reaction container, slowly adding 1-10 parts by weight of dried graphene oxide step by step, reacting at 60-80 ℃ for 1-2 hours to form a turbid liquid, adding 25-55 parts by weight of polyester polyol B, continuing at 60-80 ℃ for 1-2 hours, and cooling to normal temperature to obtain a component B;

preparing a component C:

placing 40-70 parts by weight of chain extender and 30-60 parts by weight of tertiary amine into a reaction kettle, fully dissolving and mixing for 2-4 hours at 30-50 ℃, and cooling to normal temperature to obtain the component C.

2. The preparation method of the polyurethane composition for shoes according to claim 1, wherein in the component A, the polyester polyol A is prepared by the polycondensation reaction of 1, 6-adipic acid and one or more of ethylene glycol, diethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, trimethylolpropane and glycerol to obtain the polyurethane composition with the number average molecular weight of 1000-2000.

3. The preparation method of the polyurethane composition for shoes as claimed in claim 1, wherein in the component B, the polyester polyol B is selected from one or more of 1, 6-adipic acid, ethylene glycol, diethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol, and is subjected to polycondensation reaction to obtain the polyurethane composition with the number average molecular weight of 1000-3000.

4. The preparation method of the polyurethane composition for shoes according to claim 1, wherein in the preparation of the component B, graphene oxide is prepared by a Hummers improvement method, namely, graphite powder and sodium nitrate are mixed, concentrated sulfuric acid is poured into the mixture and is uniformly stirred, potassium permanganate is added in times to react, hydrogen peroxide is added to the mixture to continue to react, and the graphene oxide is obtained after centrifugal washing and drying.

5. The preparation method of the polyurethane composition for shoes as claimed in claim 4, wherein the mass ratio of the mass of hydrogen peroxide to the mass of graphite powder is 10-30: 1.

6. the method for producing a polyurethane composition for shoes as claimed in claim 1, wherein the residual NCO group content of the B component in the production of the B component is 17 to 19% by mass.

7. The method for preparing a polyurethane composition for shoes as claimed in claim 1, wherein the chain extenders are selected from one or more of ethylene glycol, diethylene glycol, and 1, 4-butanediol.

8. The method for producing a polyurethane composition for shoes according to claim 1, wherein 0.2 to 1.5 parts by weight of a foam stabilizer is added to the component A, and the foam stabilizer is one or more selected from Dow Corning DC-193 and Meiji pattern L-1500.

9. The method of claim 1, wherein the polyisocyanate in the component B is selected from one or more of diphenylmethane diisocyanate MDI, liquefied MDI, hydrogenated MDI, toluene diisocyanate TDI, naphthalene diisocyanate NDI, isophorone isocyanate IPDI, and IPDI isomers and/or derivatives and/or modified polymers.

10. The method for producing a polyurethane composition for shoes as claimed in claim 1, wherein the production of the B-side component is carried out in the presence of phosphoric acid as a side reaction inhibitor, and the amount of the side reaction inhibitor added is 5 to 50ppm based on the total mass of the B-side component.

11. The method of claim 1, wherein the step of preparing the polyurethane composition for shoes is carried out by preparing the component C, and the tertiary amine is one or more selected from the group consisting of triethylenediamine, dimethylcyclohexylamine, N-methyldicyclohexylamine, pentamethyldipropylenetriamine, bis (dimethylaminoethyl) ether, N-methylimidazole, 1, 8-diazacycloundecene, and dibutyltin dilaurate.

12. A method for preparing a polyurethane molded body by using the polyurethane composition for shoes obtained by the method of any one of claims 1 to 11, which is characterized in that the polyurethane molded body is prepared by mixing A, B, C three components and then foaming and molding: uniformly mixing the component A and the component C at 40-60 ℃ according to the weight ratio of 100: 1-100: 3 to obtain A, C component mixture component, wherein the ratio of the mole number of active hydrogen in the mixture component to the mole number of-NCO in the component B is controlled to be 1: 1, mixing in a two-component casting machine, injecting into a mold at 40-60 ℃ for reaction for 2-5 min for molding, demolding, and post-curing in an oven at 60-70 ℃ for 24h to obtain the polyurethane molded body.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a preparation method of a polyurethane composition for shoes, a polyurethane forming body obtained from the polyurethane composition and application of the polyurethane forming body.

Background

Unlike shoes worn in daily life, which are attractive and comfortable, functional shoes used in some special occasions are more important in safety, for example, in dust-free production workshops of automobiles or electronic manufacturing, the safety shoes are required to be antistatic, prevent dust from being adsorbed by static electricity and damage dust-free environment; as a large amount of flammable and explosive chemicals exist in a chemical production workshop, the static sparks generated by the friction of the soles can cause the explosion of dangerous chemicals, and therefore the chemical production workshop also has the same antistatic requirement.

The polyurethane material has the characteristics of light weight, good elasticity, wear resistance, folding resistance, oil resistance and the like after being micro-foamed, and can be used as a shoe part or a sole material. However, because polyurethane is an insulating material and does not have an antistatic effect, ordinary polyurethane cannot meet the industry with the requirement on antistatic property, and antistatic property can be generally imparted by adding an antistatic agent. The graphene oxide has a special honeycomb two-dimensional structure, contains a large number of active groups such as hydroxyl, carboxyl, epoxy and the like on the surface and the edge, has excellent physical, chemical, optical, electrical and other properties, regulates the type and the number of oxygen-containing functional groups to modulate the conductivity and the band gap, and can be used as a performance improver of a high polymer material. However, although graphene oxide contains more active groups and has stronger reactivity than graphene, the graphene oxide still maintains the small-size effect and the surface effect of the layered nanomaterial similar to graphene, and the compatibility effect with a high polymer material is still poor, so that the performance of the material is affected. The functional shoes applied to the fields have clear requirements on antistatic performance, also have certain requirements on physical and mechanical properties of a sole material such as aging resistance, skid resistance, wear resistance, folding resistance and the like, and also have wearing comfort, so that the antistatic functional shoes in the market at present cannot achieve ideal effects.

Disclosure of Invention

The technical problem is as follows: in order to overcome the defects of the prior art, the invention provides a preparation method of a polyurethane composition for shoes and a polyurethane forming body obtained from the polyurethane composition, the polyurethane forming body prepared from the product can be used for preparing sole parts of safety shoes and safety shoes, has excellent antistatic performance, forms a stable antistatic microporous elastic structure, overcomes the defect of continuous migration of an organic antistatic agent, ensures the durability of the antistatic performance, and obviously improves the mechanical properties such as tensile strength, tearing strength and the like, wear resistance and the like.

The technical scheme is as follows: the invention discloses a preparation method of a polyurethane composition for shoes, which comprises a component A, a component B and a component C which are separated, and the preparation method comprises the following steps:

preparing a component A:

in parts by weight, 100 parts by weight of polyester polyol A and 3-10 parts by weight of chain extender are fully mixed for 2-4 hours at 30-50 ℃ in the presence of 0.1-1 part by weight of water, and then cooled to normal temperature to obtain a component A;

preparing a component B:

placing 40-80 parts by weight of polyisocyanate in a nitrogen-protected reaction container, slowly adding 1-10 parts by weight of dried graphene oxide step by step, reacting at 60-80 ℃ for 1-2 hours to form a turbid liquid, adding 25-55 parts by weight of polyester polyol B, continuing at 60-80 ℃ for 1-2 hours, and cooling to normal temperature to obtain a component B;

preparing a component C:

placing 40-70 parts by weight of chain extender and 30-60 parts by weight of tertiary amine into a reaction kettle, fully dissolving and mixing for 2-4 hours at 30-50 ℃, and cooling to normal temperature to obtain the component C.

Wherein the content of the first and second substances,

in the component A, the polyester polyol A is selected from one or a mixture of more of 1, 6-adipic acid, ethylene glycol, diethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, trimethylolpropane and glycerol, and the polyester polyol A is subjected to polycondensation reaction to obtain the polyester polyol A with the number average molecular weight of 1000-2000.

In the component B, the polyester polyol B is selected from one or a mixture of more of 1, 6-adipic acid and ethylene glycol, diethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol, and the number average molecular weight is 1000-3000.

In the preparation of the component B, graphene oxide is prepared by a Hummers improvement method, namely graphite powder and sodium nitrate are mixed, concentrated sulfuric acid is poured into the mixture and stirred uniformly, potassium permanganate is added in times to react, hydrogen peroxide is added to continue to react, and graphene oxide is obtained after centrifugal washing and drying.

The mass ratio of the hydrogen peroxide to the graphite powder is 10-30: 1.

in the preparation of the component B, the mass content of residual NCO groups of the component B is 17-19%.

The chain extender is respectively selected from one or a mixture of more of ethylene glycol, diethylene glycol and 1, 4-butanediol.

In the component A, 0.2-1.5 parts by weight of a foam stabilizer is added, and the foam stabilizer is selected from one or more of Dow Corning DC-193 and Mei Tu L-1500.

In the component B, the polyisocyanate is selected from one or more of diphenylmethane diisocyanate (MDI), liquefied MDI, hydrogenated MDI, Toluene Diisocyanate (TDI), Naphthalene Diisocyanate (NDI), isophorone isocyanate (IPDI), IPDI isomer and/or derivative and/or modified polymer.

The preparation of the component B is carried out in the presence of a side reaction inhibitor phosphoric acid, and the addition amount of the side reaction inhibitor is 5-50 ppm calculated on the basis of the total mass of the component B.

And the tertiary amine is one or a mixture of more of triethylene diamine, dimethylcyclohexylamine, N-methyldicyclohexylamine, pentamethyldipropylenetriamine, bis (dimethylaminoethyl) ether, N-methylimidazole, 1, 8-diazacycloundecylene and dibutyl tin dilaurate.

The invention discloses a method for preparing a polyurethane forming body by using a polyurethane composition for shoes, wherein the polyurethane forming body is prepared by mixing A, B, C three components and then foaming and forming: uniformly mixing the component A and the component C at 40-60 ℃ according to the weight ratio of 100: 1-100: 3 to obtain A, C component mixture component, wherein the ratio of the mole number of active hydrogen in the mixture component to the mole number of-NCO in the component B is controlled to be 1: 1, mixing in a two-component casting machine, injecting into a mold at 40-60 ℃ for reaction for 2-5 min for molding, demolding, and post-curing in an oven at 60-70 ℃ for 24h to obtain the polyurethane molded body.

The method has the beneficial effects that the density of the polyurethane forming body product obtained by the method is 0.5-0.65 g/cm³The tensile strength is 6.0-7.5 Mpa, the tear strength is 26-35 KN/m, and the DIN abrasion is 120-170 mm³The surface resistivity (23 ℃ C., 50% humidity) of the electrostatic effect reaches 10⁶～10⁸Ω。

The polyurethane formed body prepared by the product can be used for preparing sole parts of safety shoes and safety shoes, has excellent antistatic performance, forms a stable antistatic microporous elastic structure, overcomes the defect of continuous migration of an organic antistatic agent, ensures the durability of the antistatic performance, and obviously improves the mechanical properties such as tensile strength, tearing strength and the like, wear resistance and the like. The applicant unexpectedly discovers that by adopting the technical scheme of the invention, the polyurethane composition can be stably stored for a long time, in addition, the foaming forming time is short, and the production efficiency is obviously higher than that of the conventional preparation of labor insurance shoes and safety shoe soles.

Detailed Description

In the embodiment of the invention, the graphene oxide is prepared by a Hummers improved method, and the preparation steps are as follows:

placing 1g of graphite powder and 2g of sodium nitrate in an ice-water bath in the rest reactor, slowly pouring 25mL of 98% concentrated sulfuric acid, stirring, controlling the temperature to be 10-15 ℃, putting 3.5g of potassium permanganate into the reactor for multiple times within 50min, and stirring;

heating to 30-50 ℃, keeping the temperature, continuously stirring, adding 160mL of deionized water, adding 30-250 g of 30% hydrogen peroxide aqueous solution to obtain a bright yellow solution, centrifugally washing to obtain a precipitate, washing the precipitate with dilute hydrochloric acid, washing with a large amount of deionized water until the pH value of supernatant reaches 7, and drying the precipitate to obtain graphene oxide;

as an example, the mass ratio of the mass of the added hydrogen peroxide (excluding water) to the mass of the graphite powder may be 10: 1. 20: 1. 30: 1, respectively obtaining graphene oxide 1, graphene oxide 2 and graphene oxide 3;

as a comparative example, the mass ratio of the added hydrogen peroxide mass (excluding water) to the graphite powder mass was 5: 1. 40: 1, respectively obtaining graphene oxide 4 and graphene oxide 5;

the invention is further described below with reference to specific examples, but without limiting the scope of the invention.