阅读说明：本技术 用于复杂鞋底模具的聚氨酯组合料及其制备方法 (Polyurethane composite material for complex sole mold and preparation method thereof ) 是由 任明月 甘经虎 李海朝 张伟 于 2020-12-31 设计创作，主要内容包括：本发明涉及聚氨酯弹性体技术领域,具体涉及一种用于复杂鞋底模具的聚氨酯组合料及其制备方法。所述的用于复杂鞋底模具的聚氨酯组合料,由A组分和B组分组成,A组分由多元醇、扩链剂、交联剂、消泡剂、匀泡剂、催化剂和发泡剂组成,其中多元醇包括以下质量百分比的原料：聚醚酯多元醇10-50％,聚酯多元醇A50-90％,聚酯聚合物多元醇0-30％；B组分由聚醚酯多元醇、聚酯多元醇、异氰酸酯和储存稳定剂组成。本发明的用于复杂鞋底模具的聚氨酯组合料,可以有效解决具有复杂款式、花纹、排气孔等模具做出的鞋底气泡次品率过高的问题；本发明还提供其制备方法。(The invention relates to the technical field of polyurethane elastomers, in particular to a polyurethane composite material for a complex sole mold and a preparation method thereof. The polyurethane composite material for the complex sole mold consists of a component A and a component B, wherein the component A consists of polyol, a chain extender, a cross-linking agent, a defoaming agent, a foam stabilizer, a catalyst and a foaming agent, and the polyol comprises the following raw materials in percentage by mass: 10-50% of polyether ester polyol, 50-90% of polyester polyol A, and 0-30% of polyester polymer polyol; the component B consists of polyether ester polyol, polyester polyol, isocyanate and a storage stabilizer. The polyurethane combined material for the complex sole mold can effectively solve the problem of high defective rate of sole bubbles produced by molds with complex styles, patterns, exhaust holes and the like; the invention also provides a preparation method of the composition.)

1. The polyurethane composite material for the complex sole mold is characterized in that: the foaming agent consists of a component A and a component B according to the weight ratio of 100: 50-120, wherein the component A consists of polyol, a chain extender, a cross-linking agent, a defoaming agent, a foam stabilizer, a catalyst and a foaming agent, and the polyol comprises the following raw materials in percentage by mass:

10-50% of polyether ester polyol

50-90 percent of polyester polyol A

0-30% of polyester polymer polyol;

the weight percentage of the rest raw materials in the total mass of the polyol is as follows:

the component B comprises the following raw materials in percentage by mass and 10ppm of storage stabilizer:

5 to 15 percent of polyether ester polyol

15 to 40 percent of polyester polyol B

60-80% of isocyanate.

2. The polyurethane composite for a complex sole mold according to claim 1, wherein: the polyether ester polyol has the number average molecular weight of 1000-4000 and the hydroxyl value of 28-110mgKOH/g, and is prepared by the polycondensation reaction of micromolecule dihydric alcohol, micromolecule polyether polyol and adipic acid;

the micromolecular dihydric alcohol is one or more of ethylene glycol, diethylene glycol and 1, 4-butanediol;

the functionality of the small-molecule polyether polyol is 1.9-2.2, and the molecular weight is 500-1500.

3. The polyurethane composite for a complex sole mold according to claim 1, wherein: the polyester polyol A has the number average molecular weight of 1000-2500 and the hydroxyl value of 45-110mgKOH/g, and is prepared by one or more of ethylene glycol, diethylene glycol and 1, 4-butanediol and one or two of adipic acid and terephthalic acid through polycondensation;

the polyester polyol B has the number average molecular weight of 1000-3000 and the hydroxyl value of 37-110mgKOH/g, and is prepared by one or more of ethylene glycol, diethylene glycol and 1, 4-butanediol and adipic acid through polycondensation reaction.

4. The polyurethane composite for a complex sole mold according to claim 1, wherein: the polyester polymer polyol is prepared by graft copolymerization of one or two of styrene and acrylonitrile, and is based on polyester polyol with functionality of 1.9-2.2 and molecular weight of 500-2500.

5. The polyurethane composite for a complex sole mold according to claim 1, wherein: the chain extender is one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 3-propanediol, dipropylene glycol and 1, 6-hexanediol; the cross-linking agent is one or more of triethanolamine, diethanolamine, glycerol and trimethylolpropane.

6. The polyurethane composite for a complex sole mold according to claim 1, wherein: the antifoaming agent is HT-630.

7. The polyurethane composite for a complex sole mold according to claim 1, wherein: the foam stabilizer is polysiloxane-oxyalkylene block copolymer; the catalyst is tertiary amine catalyst; the foaming agent is water.

8. The polyurethane composite for a complex sole mold according to claim 1, wherein: the isocyanate is one or more of pure MDI, carbodiimide modified MDI, MDI-50 and polymeric MDI.

9. The polyurethane composite for a complex sole mold according to claim 1, wherein: the storage stabilizer is phosphoric acid or benzoyl chloride.

10. A polyurethane composite for a complex footwear sole mold according to any one of claims 1 to 9, wherein: the method comprises the following steps:

(1) a component material: adding polyether ester polyol, polyester polyol A, polyester polymer polyol, a chain extender, a cross-linking agent, a defoaming agent, a foam stabilizer, a catalyst and a foaming agent into a reaction kettle at normal temperature based on the formula amount, and stirring to obtain a component A;

(2) b, component material: putting polyether ester polyol and polyester polyol B based on formula amount into a reaction kettle at normal temperature, stirring and heating to 90-110 ℃, dehydrating and degassing for 2-3h under a vacuum condition, then cooling to below 50 ℃, adding a storage stabilizer and isocyanate, and reacting for 2-3h at 80-85 ℃ to obtain a component B;

(3) when in use, the A, B components are respectively injected into a charging bucket of a low-pressure casting machine, mixed at the nose and then injected into a mold, the mold temperature is controlled at 40-60 ℃, and the mold is opened after 4-5min to obtain the sole product.

Technical Field

The invention relates to the technical field of polyurethane elastomers, in particular to a polyurethane composite material for a complex sole mold and a preparation method thereof.

Background

The polyurethane material has the advantages of excellent physical and mechanical properties, acid and alkali corrosion resistance, high bearing performance, wide hardness range and the like, has become one of mainstream materials in the sole market, and is widely used for producing casual shoes, sports shoes, safety shoes, sandals and the like at present. At present, the sole production by using the polyurethane sole stock solution is mainly an open type reaction injection molding process, namely A, B double-component materials are accurately metered according to the proportion and sent into a mixing head to be stirred and mixed at a high speed, then the mixture is quickly injected into a sole mold, when the mixture is not foamed or begins to be foamed, the mold is closed, the polyurethane material is foamed to quickly fill the sole mold, and the polyurethane sole is obtained after curing and mold opening.

Along with the upgrading of consumption level, the complexity of styles, patterns, exhaust positions and the like of a sole mold is continuously improved, the problem of bubbles on the surface of a sole made of the existing combined material formula is prominent, the bubbles mainly appear as bubbles with different sizes from rice grains to soybean grains on the side edges, the heel and the bottom of an upper, the defective rate of the sole is too high, the design of the complicated mold style is influenced, and the bubbles become a great adverse factor for restricting the development and upgrading of the polyurethane foamed sole.

Disclosure of Invention

The invention aims to provide a polyurethane combined material for a complicated sole mold, which can effectively solve the problem of high defective rate of sole bubbles produced by molds with complicated styles, patterns, exhaust holes and the like; the invention also provides a preparation method of the composition.

The polyurethane composite material for the complex sole mold disclosed by the invention comprises a component A and a component B according to the weight ratio of 100: 50-120, wherein the component A comprises polyol, a chain extender, a cross-linking agent, a defoaming agent, a foam stabilizer, a catalyst and a foaming agent, and the polyol comprises the following raw materials in percentage by mass:

10-50% of polyether ester polyol

50-90 percent of polyester polyol A

0-30% of polyester polymer polyol;

the weight percentage of the rest raw materials in the total mass of the polyol is as follows:

the component B comprises the following raw materials in percentage by mass and 10ppm of storage stabilizer:

5 to 15 percent of polyether ester polyol

15 to 40 percent of polyester polyol B

60-80% of isocyanate.

The number average molecular weight of the polyether ester polyol is 1000-4000, and the hydroxyl value is 28-110 mgKOH/g; prepared by the polycondensation of micromolecular dihydric alcohol, micromolecular polyether glycol and adipic acid; the micromolecular dihydric alcohol is one or more of ethylene glycol, diethylene glycol and 1, 4-butanediol; the functionality of the small-molecule polyether polyol is 1.9-2.2, and the molecular weight is 500-1500.

The polyester polyol A has the number average molecular weight of 1000-; prepared by one or more of ethylene glycol, diethylene glycol and 1, 4-butanediol and one or two of adipic acid and terephthalic acid through polycondensation reaction.

The number average molecular weight of the polyester polyol B is 1000-3000, and the hydroxyl value is 37-110 mgKOH/g; prepared by one or more of ethylene glycol, diethylene glycol and 1, 4-butanediol and adipic acid through polycondensation reaction.

The polyester polymer polyol is prepared by graft copolymerization of one or two of styrene and acrylonitrile, and is based on polyester polyol with functionality of 1.9-2.2 and molecular weight of 500-2500.

The chain extender is one or more of Ethylene Glycol (EG), diethylene glycol (DEG), 1, 4-butanediol (1,4-BG), 1, 3-propylene glycol (1,3-PDO), dipropylene glycol (DPG) and 1, 6-hexanediol.

The crosslinking agent is one or more of Triethanolamine (TEA), Diethanolamine (DEOA), glycerol, and trimethylolpropane.

The antifoaming agent is HT-630, produced by break Tai chemical industry Co., Ltd.

The foam stabilizer is a polysiloxane-oxyalkylene block copolymer, preferably DC-193 from air chemical products, Inc., USA.

The catalyst is tertiary amine catalyst, preferably A33 (33% ethylene glycol solution of triethylene diamine).

The foaming agent is water.

The isocyanate is one or more of pure MDI, carbodiimide modified MDI, MDI-50 and polymeric MDI.

The storage stabilizer is phosphoric acid or benzoyl chloride.

The sole produced by using the complex sole mould is easy to generate bubbles with different sizes at positions with unsmooth air exhaust, such as corner bending, sharp corners of patterns, the upper part of the heel and the like, so that the defective rate of the sole is overhigh. According to the invention, after the defoaming agent HT-630 is added into the component A of the sole stock solution, bubbles of a complex sole mold can be effectively eliminated, and other properties of the sole are not affected. The complex sole mold comprises but is not limited to a sole mold with a heel thickness larger than 1cm and an outward bulge in the middle of the heel, a mold with an exhaust hole in the middle of the outer side surface and the lower part including the bottom of the sole, a sole mold with a shock-absorbing air cushion in the heel of the sole and the like.

The invention relates to a polyurethane composite material for a complex sole mold, which comprises the following steps:

(1) a component material: adding polyether ester polyol, polyester polyol A, polyester polymer polyol, a chain extender, a cross-linking agent, a defoaming agent, a foam stabilizer, a catalyst and a foaming agent into a reaction kettle at normal temperature based on the formula amount, and stirring to obtain a component A;

(2) b, component material: putting polyether ester polyol and polyester polyol B based on formula amount into a reaction kettle at normal temperature, stirring and heating to 90-110 ℃, dehydrating and degassing for 2-3h under a vacuum condition, then cooling to below 50 ℃, adding a storage stabilizer and isocyanate, and reacting for 2-3h at 80-85 ℃ to obtain a component B;

(3) when in use, the A, B components are respectively injected into a charging bucket of a low-pressure casting machine, mixed at the nose and then injected into a mold, the mold temperature is controlled at 40-60 ℃, and the mold is opened after 4-5min to obtain the sole product.

Compared with the prior art, the invention has the following beneficial effects:

(1) according to the invention, the defoaming agent HT-630 is added into the component A of the sole stock solution, and is matched with the polyether ester component synthesized by taking micromolecular polyether as a raw material in the formula, so that bubbles of a complex sole mould can be effectively eliminated, and the problem of high defective rate of sole bubbles produced by moulds with complex styles, patterns, exhaust holes and the like is effectively solved;

(2) the method does not need to add extra cost and operation steps, and has low economic cost.

Detailed Description

In order to facilitate understanding of the present invention, the present invention will be described below by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The percentages in the examples are mass percentages, the total mass of the polyhydric alcohols in the component A is 100%, and the consumption of the rest raw materials is the percentage of the polyhydric alcohols.

Example 1

The component A comprises:

and B component:

the preparation method comprises the following steps:

(1) a component material: polyether polyol with the molecular weight of 500 and the functionality of 2.0, ethylene glycol, diethylene glycol and adipic acid are subjected to polycondensation reaction according to the molar ratio of 30:40:40:100 to prepare polyether ester polyol with the number average molecular weight of 2500, the hydroxyl value of 45mgKOH/g and the functionality of 2.0; performing polycondensation reaction on ethylene glycol, diethylene glycol, 1, 4-butanediol and adipic acid according to a molar ratio of 30:30:50:100 to obtain polyester polyol A with the number average molecular weight of 1000, the hydroxyl value of 110mgKOH/g and the functionality of 2.0; taking polyester polyol with functionality of 2.2 and molecular weight of 1500 as basic polyester, and graft polymerizing with styrene to obtain polyester polymer polyol with hydroxyl value of 50mgKOH/g and solid content of 15%; putting all raw materials based on the formula amount into a reaction kettle at normal temperature, and uniformly stirring to obtain a component A;

(2) b, component material: preparing polyester polyol B with number average molecular weight of 2500, hydroxyl value of 45mgKOH/g and functionality of 2.0 by using ethylene glycol, 1, 4-butanediol and adipic acid according to a molar ratio of 45:60:100 through a polycondensation reaction, putting polyether polyol and polyester polyol B based on formula amount into a reaction kettle at normal temperature, stirring and heating to 100 ℃, dehydrating and degassing for 2h under a vacuum condition, then cooling to 50 ℃, adding 10ppm phosphoric acid and pure MDI with the formula ratio, and reacting for 2h at 80 ℃ to obtain a component B;

(3) when the sole is used, the component A and the component B are respectively injected into a charging bucket of a low-pressure casting machine, a sole mold with the heel thickness larger than 1cm and the middle part of the heel protruding outwards is injected after the components A, B and C are mixed at the head according to the proportion of 100:75, the temperature of the mold is kept at 50 ℃, the mold is opened after 5 minutes, the sole is obtained by molding, the sole is placed on a bright place to observe the surface, and all visible surfaces have no bubbles visible to naked eyes.

Example 2

The component A comprises:

and B component:

the preparation method comprises the following steps:

(1) a component material: polyether polyol with the molecular weight of 1500 and the functionality of 2.0, diethylene glycol and adipic acid are subjected to polycondensation reaction according to the molar ratio of 20:90:100 to prepare polyether ester polyol with the number average molecular weight of 3000, the hydroxyl value of 37mgKOH/g and the functionality of 2.0; performing polycondensation reaction on ethylene glycol, diethylene glycol and adipic acid according to a molar ratio of 30:80:100 to obtain polyester polyol A with a number average molecular weight of 3500, a hydroxyl value of 32mgKOH/g and a functionality of 2.0; putting all raw materials based on the formula amount into a reaction kettle at normal temperature, and uniformly stirring to obtain a component A;

(2) b, component material: carrying out polycondensation reaction on 1, 4-butanediol and adipic acid according to a molar ratio of 110:100 to obtain polyester polyol B with the number average molecular weight of 1000, the hydroxyl value of 110mgKOH/g and the functionality of 2.0, putting polyether polyol and the polyester polyol B based on the formula amount into a reaction kettle at normal temperature, stirring and heating to 100 ℃, dehydrating and degassing for 2h under the vacuum condition, cooling to 50 ℃, adding 10ppm benzoyl chloride and pure MDI according to the formula ratio, and reacting for 2h at 80 ℃ to obtain a component B;

(3) when the sole is used, the component A and the component B are respectively injected into a charging bucket of a low-pressure casting machine, mixed at a machine head according to the proportion of A: B being 100:65, and then injected into a mold with an exhaust hole positioned in the middle of the outer side surface and the part below the exhaust hole and including the bottom of the sole, the temperature of the mold is kept at 55 ℃, the mold is opened after 5 minutes, the sole is obtained by molding, the sole is placed at a bright place to observe the surface, and all visible surfaces have no bubbles visible to naked eyes.

Example 3

The component A comprises:

and B component:

the preparation method comprises the following steps:

(1) a component material: polyether polyol with the molecular weight of 700 and the functionality of 2.0, ethylene glycol, diethylene glycol and adipic acid are subjected to polycondensation reaction according to the molar ratio of 40:20:30:100 to prepare polyether ester polyol with the number average molecular weight of 1800, the hydroxyl value of 62mgKOH/g and the functionality of 2.0; performing polycondensation reaction on ethylene glycol, 1, 4-butanediol, adipic acid and terephthalic acid according to a molar ratio of 70:40:80:20 to obtain polyester polyol A with the number average molecular weight of 2000, the hydroxyl value of 56mgKOH/g and the functionality of 2.0; taking polyester polyol with functionality of 2.0 and molecular weight of 800 as basic polyester, and preparing polyester polymer polyol with hydroxyl value of 55mgKOH/g and solid content of 20% by styrene graft polymerization; putting all raw materials based on the formula amount into a reaction kettle at normal temperature, and uniformly stirring to obtain a component A;

b, component material: preparing polyester polyol B with the number average molecular weight of 2000, the hydroxyl value of 56mgKOH/g and the functionality of 2.0 by using ethylene glycol, diethylene glycol, 1, 4-butanediol and adipic acid according to the molar ratio of 65:20:20:100 through a polycondensation reaction, putting polyether polyol and polyester polyol B based on the formula amount into a reaction kettle at normal temperature, stirring and heating to 100 ℃, dehydrating and degassing for 2h under a vacuum condition, then cooling to 50 ℃, adding 10ppm phosphoric acid and pure MDI according to the formula ratio, and reacting for 2h at 80 ℃ to obtain a component B;

(3) when the sole is used, the component A and the component B are respectively injected into a charging bucket of a low-pressure casting machine, the components A, B and B are mixed at a machine head according to the proportion of 100:60, then the mixture is injected into a sole mold which can be used for placing a shock-absorbing air cushion at the heel part of the sole, the temperature of the mold is kept at 50 ℃, the mold is opened after 5 minutes, the sole is obtained by molding, the sole is placed at a bright place to observe the surface, and all visible surfaces have no bubbles visible to naked eyes.

Comparative example 1

In the same manner as in example 1, except that the antifoaming agent HT-630 was removed, no change was made, and the surface of the obtained shoe sole was observed to have significant bubbles.

Comparative example 2

In the same manner as in example 1, in component A, the same amount of polyester polyol A was used instead of polyetherester polyol, and in component B, the same amount of polyester polyol B was used instead of polyetherester polyol, and in all cases, significant bubbles were observed on the surface of the resulting shoe sole.

Comparative example 3

In the same manner as in example 2, the defoaming agent HT-630 was removed, and the surface of the obtained shoe sole was observed to have significant bubbles.

Comparative example 4

In the same manner as in example 2, in component A, the same amount of polyester polyol A was used instead of polyetherester polyol, and in component B, the same amount of polyester polyol B was used instead of polyetherester polyol, and in all cases, significant bubbles were observed on the surface of the resulting shoe sole.

Comparative example 5

In the same manner as in example 3, the defoaming agent HT-630 was removed, and the surface of the obtained shoe sole was observed to have significant bubbles.

Comparative example 6

In the same manner as in example 3, in component A, the same amount of polyester polyol A was used instead of polyetherester polyol, and in component B, the same amount of polyester polyol B was used instead of polyetherester polyol, and in all cases, significant bubbles were observed on the surface of the resulting shoe sole.

The soles prepared in examples 1-3 and comparative examples 1-6 were subjected to a performance test in which the density of the test specimens was determined according to GB/T6343-1995; the hardness is measured according to GB/T531-1999 standard; the tensile strength and the elongation are determined according to GB/T528-2009 standard; the right-angle tear strength is measured according to the GB/T529-2008 standard; the outsole folding endurance was measured according to GB/T20991-2007 standard, and the test results are shown in Table 1.

TABLE 1 results of performance test of soles prepared in examples 1 to 3 and comparative examples 1 to 6