High-hardness polyurethane composite material and preparation method thereof

文档序号：526421 发布日期：2021-06-01 浏览：14次中文

阅读说明：本技术 高硬度聚氨酯复合材料及其制备方法 (High-hardness polyurethane composite material and preparation method thereof ) 是由孙立胜傅运军高鹏柳尧辉于 2021-01-16 设计创作，主要内容包括：本申请涉及聚氨酯的技术领域,尤其涉及一种高硬度聚氨酯复合材料及其制备方法；高硬度聚氨酯复合材料,通过预聚原料和扩链原料反应而得；所述预聚原料包括聚合物多元醇以及二异氰酸酯,所述扩链原料包括扩链剂以及催化剂；所述聚合物多元醇包括聚酯多元醇或聚醚多元醇；所述二异氰酸酯包括二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、二甲基联苯二异氰酸酯或对苯二异氰酸酯。高硬度聚氨酯复合材料的制备方法,通过制备预聚体和扩链料,之后将两者混合并加热反应制得高硬度聚氨酯复合材料。本申请所制得的聚氨酯复合材料具有良好的硬度、力学强度以及耐磨性；其中,聚氨酯复合材料的硬度均大于88A。(The application relates to the technical field of polyurethane, in particular to a high-hardness polyurethane composite material and a preparation method thereof; the high-hardness polyurethane composite material is obtained by reacting a prepolymerization raw material and a chain extension raw material; the prepolymerization raw material comprises polymer polyol and diisocyanate, and the chain extension raw material comprises a chain extender and a catalyst; the polymer polyol comprises a polyester polyol or a polyether polyol; the diisocyanate includes diphenylmethane diisocyanate, toluene diisocyanate, dimethylbiphenyl diisocyanate, or p-phenylene diisocyanate. The preparation method of the high-hardness polyurethane composite material comprises the steps of preparing a prepolymer and a chain extender, mixing the prepolymer and the chain extender, and heating to react to prepare the high-hardness polyurethane composite material. The polyurethane composite material prepared by the method has good hardness, mechanical strength and wear resistance; wherein the hardness of the polyurethane composite material is more than 88A.)

1. The high-hardness polyurethane composite material is characterized in that: obtained by the reaction of a prepolymerization raw material and a chain extension raw material; the prepolymerization raw material comprises polymer polyol and diisocyanate, and the chain extension raw material comprises a chain extender and a catalyst;

the polymer polyol comprises a polyester polyol or a polyether polyol; the diisocyanate includes diphenylmethane diisocyanate, toluene diisocyanate, dimethylbiphenyl diisocyanate, or p-phenylene diisocyanate.

2. The high-hardness polyurethane composite according to claim 1, wherein: the prepolymerization raw material also comprises a cross-linking agent; the chain extension raw materials also comprise acetal resin, silicon nitride, ceramic powder, a defoaming agent and an antioxidant.

3. The high-hardness polyurethane composite according to claim 2, wherein: the prepolymerization raw material comprises 100 parts by mass of polymer polyol, 100 parts by mass of diisocyanate and 1-3 parts by mass of cross-linking agent; the chain extension raw material comprises 18-25 parts by mass of a chain extender, 6-12 parts by mass of acetal resin, 3-8 parts by mass of silicon nitride, 5-10 parts by mass of ceramic powder, 0.1-0.5 part by mass of a catalyst, 0.5-1 part by mass of a defoaming agent and 1-5 parts by mass of an antioxidant.

4. The high-hardness polyurethane composite according to claim 3, wherein: the polyester polyol comprises polypropylene carbonate diol, polycaprolactone diol or poly-1, 4-butanediol adipate diol; the polyether polyol comprises polypropylene glycol or polytetrahydrofuran ether glycol.

5. The high-hardness polyurethane composite according to claim 3, wherein: the chain extender is 3,3 '-dichloro-4, 4' -diaminodiphenylmethane or 1, 4-butanediol.

6. The high-hardness polyurethane composite according to claim 3, wherein: the catalyst is triethylene diamine or dibutyltin dilaurate.

7. The method for preparing a high-hardness polyurethane composite material according to any one of claims 1 to 6, wherein: the method comprises the following steps:

1) dehydrating the polymer polyol and the diisocyanate; then mixing the two under the protection of nitrogen; then heating and reacting to obtain a prepolymer;

2) uniformly mixing a chain extender and a catalyst, and dehydrating to obtain a chain extender;

3) and mixing the prepolymer and the chain extender, and heating for reaction to obtain a finished product.

8. The method for preparing a high-hardness polyurethane composite material according to claim 7, wherein: in the step 1), the polymer polyol and the diisocyanate are respectively heated to 105-115 ℃ and dehydrated in vacuum for 1-3h, and then cooled to room temperature; under the protection of nitrogen, dripping the dehydrated diisocyanate into the dehydrated polymer polyol and stirring; then heating to 75-85 ℃, and then preserving the heat for 2-4h to obtain the prepolymer.

9. The method for preparing a high-hardness polyurethane composite material according to claim 7, wherein: in the step 2), uniformly mixing the chain extender and the catalyst; heating to 70-80 deg.C, vacuum dehydrating, and keeping the temperature for 2-4 h; and then cooling to obtain the chain extender.

10. The method for preparing a high-hardness polyurethane composite material according to claim 7, wherein: in the step 3), the prepolymer and the chain extender are quickly and uniformly mixed at a stirring speed of 2000-5000 r/m; then injecting the mixture into a mold at the temperature of between 90 and 110 ℃, heating the mixture to 115 and 130 ℃ for curing, and curing the mixture to obtain a finished product.

Technical Field

The application relates to the technical field of polyurethane, in particular to a high-hardness polyurethane composite material and a preparation method thereof.

Background

Polyurethane is also called polyurethane, and is a polymer containing amino and formate groups in a molecular main chain; the polyurethane material has excellent characteristics of wear resistance, oil resistance, adjustable hardness, strong designability and the like, and is widely applied to various fields.

At present, in the related technology, a polyurethane material is obtained through prepolymer synthesis and chain extension reaction, and the hardness of the polyurethane material can be adjusted through adjusting the proportion of raw materials; the Shore hardness of the polyurethane material with higher hardness can reach about 85A, and the polyurethane material can be used for sieve plates, shaking tables, cleaning pipes, sliding plate wheels and the like.

In view of the above-mentioned related arts, the inventors believe that the polyurethane material in the related art, although having a good hardness, is not suitable for applications in fields requiring higher hardness, such as casters, idlers, and steel rollers.

Disclosure of Invention

Aiming at the defects in the related art, the application provides a high-hardness polyurethane composite material and a preparation method thereof in order to endow the polyurethane composite material with higher hardness.

In a first aspect, the application provides a high-hardness polyurethane composite material, which adopts the following technical scheme:

the high-hardness polyurethane composite material is obtained by reacting a prepolymerization raw material and a chain extension raw material; the prepolymerization raw material comprises polymer polyol and diisocyanate, and the chain extension raw material comprises a chain extender and a catalyst;

By adopting the technical scheme, the diphenylmethane diisocyanate, the toluene diisocyanate, the dimethyl biphenyl diisocyanate and the p-phenylene diisocyanate are used as the hard segment part of the molecular chain of the polyurethane material, so that the prepared polyurethane material can be endowed with higher hardness.

Optionally, the prepolymerization raw material further comprises a cross-linking agent; the chain extension raw materials also comprise acetal resin, silicon nitride, ceramic powder, a defoaming agent and an antioxidant.

By adopting the technical scheme, the cross-linking agent can improve the cross-linking degree of the prepared polyurethane material, so that the mechanical strength and hardness of the polyurethane material are improved. The acetal resin, the silicon nitride and the ceramic powder have good hardness, and are beneficial to improving the mechanical property of the polyurethane.

Optionally, the prepolymerization raw material comprises 100 parts by mass of polymer polyol, 100-150 parts by mass of diisocyanate and 1-3 parts by mass of cross-linking agent; the chain extension raw material comprises 18-25 parts by mass of a chain extender, 6-12 parts by mass of acetal resin, 3-8 parts by mass of silicon nitride, 5-10 parts by mass of ceramic powder, 0.1-0.5 part by mass of a catalyst, 0.5-1 part by mass of a defoaming agent and 1-5 parts by mass of an antioxidant.

By adopting the technical scheme, the polyurethane composite material is endowed with higher hardness, good wear resistance and mechanical strength through the compatibility of the raw material components.

Optionally, the polyester polyol comprises polypropylene carbonate diol, polycaprolactone diol, or poly-1, 4-butylene adipate diol; the polyether polyol comprises polypropylene glycol or polytetrahydrofuran ether glycol.

By adopting the technical scheme, the poly (propylene carbonate) glycol, the polycaprolactone glycol, the poly (1, 4-butylene adipate) glycol, the polypropylene glycol and the polytetrahydrofuran ether glycol can well participate in the synthesis of polyurethane, so that the polyurethane composite material can be successfully synthesized and has good performance.

Optionally, the chain extender is 3,3 '-dichloro-4, 4' -diaminodiphenylmethane or 1, 4-butanediol.

By adopting the technical scheme, 3,3 '-dichloro-4, 4' -diaminodiphenylmethane and 1, 4-butanediol can both well ensure that the chain extension reaction is smoothly carried out, and guarantee is provided for the synthesis of the polyurethane composite material.

Optionally, the catalyst is triethylene diamine or dibutyltin dilaurate.

By adopting the technical scheme, the triethylene diamine and the dibutyltin dilaurate can promote the smooth synthesis reaction of polyurethane.

In a second aspect, the present application provides a method for preparing a high hardness polyurethane composite material, which adopts the following technical scheme:

the preparation method of the high-hardness polyurethane composite material comprises the following steps:

1) dehydrating the polymer polyol and the diisocyanate; then mixing the two under the protection of nitrogen; then heating and reacting to obtain a prepolymer;

2) uniformly mixing a chain extender and a catalyst, and dehydrating to obtain a chain extender;

3) and mixing the prepolymer and the chain extender, and heating for reaction to obtain a finished product.

By adopting the technical scheme, the polyurethane composite material with high hardness can be synthesized smoothly.

Optionally, in the step 1), the polymer polyol and the diisocyanate are respectively heated to 105-115 ℃ and vacuum dehydrated for 1-3h, and then cooled to room temperature; under the protection of nitrogen, dripping the dehydrated diisocyanate into the dehydrated polymer polyol and stirring; then heating to 75-85 ℃, and then preserving the heat for 2-4h to obtain the prepolymer.

By adopting the technical scheme, the reaction of isocyanate and water can be reduced through heating and vacuum dehydration, and the possibility of abnormal increase of the viscosity of the prepolymer is reduced, so that the smooth synthesis of the polyurethane material is facilitated. Meanwhile, nitrogen protection is adopted, so that the reaction of isocyanate and moisture in the air is reduced, and the smooth synthesis of the polyurethane material is promoted.

Optionally, in the step 2), the chain extender and the catalyst are uniformly mixed; heating to 70-80 deg.C, vacuum dehydrating, and keeping the temperature for 2-4 h; and then cooling to obtain the chain extender.

By adopting the technical scheme, the raw materials are dehydrated, and the reaction of isocyanate and water is reduced, so that the smooth synthesis of the polyurethane composite material and the improvement of the performance of the polyurethane composite material are facilitated.

Optionally, in the step 3), the prepolymer and the chain extender are rapidly and uniformly mixed at a stirring speed of 2000-; then injecting the mixture into a mold at the temperature of between 90 and 110 ℃, heating the mixture to 115 and 130 ℃ for curing, and curing the mixture to obtain a finished product.

By adopting the technical scheme, the prepolymer and the chain extender react, and the chain extender promotes the chain extension reaction of the prepolymer and endows the prepared polyurethane composite material with good performance.

In summary, the present application includes at least one of the following beneficial effects:

1. the polyurethane composite material prepared by the method has good hardness, mechanical strength and wear resistance; wherein the hardness of the polyurethane composite material is more than 88A.

2. According to the preparation method, the cross-linking degree of the molecular chain of the polyurethane composite material is improved through the introduction of the cross-linking agent and the mutual action of the cross-linking agent, the polymer polyol and the diisocyanate, so that the hardness and the mechanical strength of the polyurethane composite material are improved.

3. The mechanical property of the polyurethane is improved by introducing acetal resin, silicon nitride and ceramic powder and matching with other raw material components.

Detailed Description

The present application will be described in further detail with reference to examples.

In the prior art, the Shore hardness of the polyurethane material with higher hardness is about 85A, and the polyurethane material can be well applied to the fields of sieve plates, shaking tables, cleaning pipes, sliding plate wheels and the like; but the method is not suitable for the fields with higher requirements on hardness, such as trundles, carrier rollers, steel rolling rods and the like.

Based on the problem, the inventor prepares the polyurethane material with the hardness of more than 89A by selecting diisocyanate, adding a cross-linking agent, acetal resin, silicon nitride and ceramic powder, adjusting the compatibility of the materials and controlling the process during preparation.

Among the raw materials used in the examples:

the poly (propylene carbonate) glycol is purchased from environmental protection science and technology of Guangdong Dalzhi GmbH, and has a molecular weight of 2000, a hydroxyl value of 54-56mg KOH/g, and a viscosity of 1400-1800mPa & s (40 ℃); polycaprolactone diol is purchased from Hunan Polyben chemical new materials science and technology Co., Ltd, has the molecular weight of 1000, the hydroxyl value of 108-116mg KOH/g, the acid value of less than 0.25mg KOH/g and the viscosity of 125mPa & s (65 ℃); the poly-1, 4-butanediol adipate glycol is purchased from bright Huiyang New Material Co, Xuzhou, and has the molecular weight of 1000, the hydroxyl value of 106-118mg KOH/g and the acid value of less than or equal to 0.5mg KOH/g; the polypropylene glycol is purchased from Nantong Runzhou chemical Co., Ltd, the molecular weight is 1000, the hydroxyl value is 102-125mg KOH/g, and the acid value is less than or equal to 0.5mg KOH/g; polytetrahydrofuran ether glycol was purchased from commercial GmbH of Jinan Peng, molecular weight 950-1050, hydroxyl number 107-117mg KOH/g, and acid number < 0.005 mg KOH/g.

Diphenylmethane diisocyanate (MDI) was purchased from Nantong Runzi chemical Co., Ltd and had a density of 1.04g/cm³Model number is PM 200; toluene Diisocyanate (TDI) was purchased from Nantong Runzhou chemical Co., Ltd and had a density of 1.14g/cm³Type TDI 80; 3,3' -Dimethylbiphenyl-4, 4-diisocyanate (TODI) was obtained from Guangzhou Haoyita New Material science and technology GmbH and had a density of 1.20g/cm³(ii) a P-phenylene diisocyanate (PPDI) was purchased from Hubei Xinkang pharmaceutical chemical Co., Ltd, and the density was 1.17g/cm³。

Acetal resin purchased from Yingcang plastification Co., Ltd, Yuyao, Rockwell hardness 94A, density 1.41g/cm³The tensile strength was 61 MPa.

Example 1

The embodiment of the application discloses a high-hardness polyurethane composite material which is obtained by mixing and reacting a prepolymerization raw material and a chain extension raw material.

Wherein, the prepolymerization raw material comprises 100Kg of polypropylene carbonate glycol, 110Kg of diphenylmethane diisocyanate and 2Kg of triethanolamine.

The poly (propylene carbonate) glycol is a polycarbonate polyol, has excellent cohesion and is beneficial to improving the mechanical strength and hardness of the prepared polyurethane material; and simultaneously has good wear resistance. The diphenylmethane diisocyanate is used as a hard segment component of the polyurethane material, and can endow the polyurethane material with higher hardness. The triethanolamine serving as the cross-linking agent can improve the cross-linking degree of the prepared polyurethane material, so that the mechanical property and the hardness of the polyurethane material are improved.

The chain extension raw materials comprise 22Kg of 1, 4-butanediol, 10Kg of acetal resin, 6Kg of silicon nitride, 7Kg of ceramic powder, 0.3Kg of triethylene diamine, 0.8Kg of organosilicon surfactant and 3Kg of oxidant 1010.

The 1, 4-butanediol plays a role of a chain extender in the preparation of polyurethane. The acetal resin has high hardness, strength, modulus and abrasion resistance, the Rockwell hardness of the acetal resin can reach 94, and the hardness and mechanical strength of the polyurethane can be improved. Triethylene diamine acts as a catalyst, and the silicone surfactant acts as a defoamer. The addition of silicon nitride and ceramic powder can be beneficial to improving the hardness of polyurethane.

The embodiment of the application also discloses a preparation method of the high-hardness polyurethane composite material, which comprises the following steps:

1) weighing the following components in proportion: 100Kg of polypropylene carbonate glycol, 110Kg of diphenylmethane diisocyanate, 2Kg of triethanolamine, 22Kg of 1, 4-butanediol, 10Kg of acetal resin, 6Kg of silicon nitride, 7Kg of ceramic powder, 0.3Kg of triethylene diamine, 0.8Kg of organosilicon surfactant and 10103 Kg of oxidant.

2) Respectively heating the polypropylene carbonate glycol, the diphenylmethane diisocyanate and the triethanolamine to 110 ℃, vacuumizing, performing vacuum dehydration for 3h (the relative vacuum degree is-0.09 Mpa), and then cooling to room temperature for later use; dripping the dehydrated diphenylmethane diisocyanate into the dehydrated polypropylene carbonate glycol at room temperature under the protection of nitrogen, and stirring to make the mixture uniform, wherein the dripping time is controlled to be 2 hours; adding triethanolamine after the dropwise addition is finished and stirring uniformly; then heating to 85 ℃, and preserving the heat for 3 hours to obtain a prepolymer; the prepolymer is sealed and stored for later use.

3) Uniformly mixing 1, 4-butanediol, acetal resin, silicon nitride, ceramic powder, triethylene diamine, an organosilicon surfactant and an oxidant 1010 at 40 ℃; heating to 80 deg.C, removing water under vacuum (relative vacuum degree of-0.09 Mpa), and maintaining the temperature for 3 hr; then cooling to 35 ℃ and discharging to obtain a chain extender; and sealing and storing the obtained chain extender for later use.

4) Rapidly and uniformly mixing the prepolymer and the chain extender at the stirring speed of 5000r/m at the temperature of 35 ℃; then injecting into a mold with the temperature of 100 ℃, heating to 120 ℃, curing for 24h, and curing for 8h at the temperature of 105 ℃ to obtain a finished product.

Example 2

Wherein, the prepolymerization raw materials comprise 100Kg of polycaprolactone diol, 100Kg of toluene diisocyanate and 2Kg of triethanolamine.

Like diphenylmethane diisocyanate, toluene diisocyanate as a hard segment component of the polyurethane material can impart higher hardness to the polyurethane material.

The chain extension raw materials comprise 18Kg of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, 8Kg of acetal resin, 5Kg of silicon nitride, 8Kg of ceramic powder, 0.2Kg of dibutyltin dilaurate, 0.5Kg of organosilicon surfactant and 1Kg of oxidant 1076.

3,3 '-dichloro-4, 4' -diaminodiphenylmethane, like 1, 4-butanediol, acts as a chain extender in the preparation of polyurethanes. Dibutyltin dilaurate acts as a catalyst in the preparation of polyurethanes.

The embodiment of the application also discloses a preparation method of the high-hardness polyurethane composite material, which comprises the following steps:

1) weighing the following components in proportion: 100Kg of polycaprolactone diol, 100Kg of toluene diisocyanate, 2Kg of triethanolamine, 18Kg of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, 8Kg of acetal resin, 5Kg of silicon nitride, 8Kg of ceramic powder, 0.2Kg of dibutyltin dilaurate, 0.5Kg of organosilicon surfactant and 10761 Kg of oxidizing agent.

2) Respectively heating polycaprolactone diol, toluene diisocyanate and triethanolamine to 110 ℃, vacuumizing, performing vacuum dehydration for 3h (the relative vacuum degree is-0.09 Mpa), and cooling to room temperature for later use; under the protection of nitrogen at room temperature, dripping the dehydrated toluene diisocyanate into the dehydrated polycaprolactone diol and stirring to make the dehydrated polycaprolactone diol uniform, wherein the dripping time is controlled to be 1 h; adding triethanolamine after the dropwise addition is finished and stirring uniformly; then heating to 85 ℃, and preserving the heat for 4 hours to obtain a prepolymer; the prepolymer is sealed and stored for later use.

3) Uniformly mixing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, acetal resin, silicon nitride, ceramic powder, dibutyltin dilaurate, an organic silicon surfactant and an oxidizing agent 1076 at the temperature of 35 ℃; heating to 70 deg.C, removing water under vacuum (relative vacuum degree of-0.09 Mpa), and keeping the temperature for 4 hr; then cooling to 35 ℃ and discharging to obtain a chain extender; and sealing and storing the obtained chain extender for later use.

4) Rapidly and uniformly mixing the prepolymer and the chain extender at a stirring speed of 4000r/m at the temperature of 35 ℃; then injecting into a mold with the temperature of 100 ℃, heating to 120 ℃, curing for 20h, and curing for 8h at the temperature of 105 ℃ to obtain a finished product.

Example 3

Wherein, the prepolymerization raw material comprises 100Kg of poly adipic acid-1, 4-butanediol ester diol, 130Kg of toluene diisocyanate and 3Kg of triethanolamine.

The chain extension raw materials comprise 20Kg of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, 6Kg of acetal resin, 4Kg of silicon nitride, 9Kg of ceramic powder, 0.1Kg of triethylene diamine, 0.6Kg of organosilicon surfactant and 1Kg of oxidant 1010.

The embodiment of the application also discloses a preparation method of the high-hardness polyurethane composite material, which comprises the following steps:

1) weighing the following components in proportion: 100Kg of poly adipic acid-1, 4-butanediol ester diol, 130Kg of toluene diisocyanate, 3Kg of triethanolamine, 20Kg of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, 6Kg of acetal resin, 4Kg of silicon nitride, 9Kg of ceramic powder, 0.1Kg of triethylene diamine, 0.6Kg of organosilicon surfactant and 10101 Kg of oxidant.

2) Respectively heating 1, 4-butanediol adipate, toluene diisocyanate and triethanolamine to 115 ℃, vacuumizing for vacuum dehydration for 1h (the relative vacuum degree is-0.09 Mpa), and cooling to room temperature for later use; under the protection of nitrogen at room temperature, dropwise adding the dehydrated toluene diisocyanate into the dehydrated poly adipic acid-1, 4-butanediol ester diol, and stirring to make the mixture uniform, wherein the dropwise adding time is controlled to be 1 h; adding triethanolamine after the dropwise addition is finished and stirring uniformly; then heating to 75 ℃, and preserving the temperature for 4 hours to obtain a prepolymer; the prepolymer is sealed and stored for later use.

3) Uniformly mixing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, acetal resin, silicon nitride, ceramic powder, triethylene diamine, an organosilicon surfactant and an oxidant 1010 at 40 ℃; heating to 80 deg.C, removing water under vacuum (relative vacuum degree of-0.09 Mpa), and keeping the temperature for 2 hr; then cooling to 35 ℃ and discharging to obtain a chain extender; and sealing and storing the obtained chain extender for later use.

4) Rapidly and uniformly mixing the prepolymer and the chain extender at a stirring speed of 4000r/m at the temperature of 35 ℃; then injecting into a mold at 105 ℃, heating to 130 ℃, curing for 16h, and curing at 105 ℃ for 5h to obtain a finished product.

Example 4

Wherein, the prepolymerization raw material comprises 100Kg of polypropylene glycol, 150Kg of toluene diisocyanate and 1Kg of triethanolamine.

The chain extension raw materials comprise 25Kg of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, 12Kg of acetal resin, 3Kg of silicon nitride, 10Kg of ceramic powder, 0.5Kg of dibutyltin dilaurate, 1Kg of organosilicon surfactant and 5Kg of oxidant 1076.

The embodiment of the application also discloses a preparation method of the high-hardness polyurethane composite material, which comprises the following steps:

1) weighing the following components in proportion: 100Kg of polypropylene glycol, 150Kg of toluene diisocyanate, 1Kg of triethanolamine, 25Kg of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, 12Kg of acetal resin, 3Kg of silicon nitride, 10Kg of ceramic powder, 0.5Kg of dibutyltin dilaurate, 1Kg of organosilicon surfactant and 10765 Kg of oxidizing agent.

2) Respectively heating polypropylene glycol, toluene diisocyanate and triethanolamine to 105 deg.C, vacuumizing, vacuum dehydrating for 3 hr (relative vacuum degree of-0.09 Mpa), and cooling to room temperature; under the protection of nitrogen at room temperature, dropwise adding the dehydrated toluene diisocyanate into the dehydrated polypropylene glycol, and stirring to make the toluene diisocyanate uniform, wherein the dropwise adding time is controlled to be 3 hours; adding triethanolamine after the dropwise addition is finished and stirring uniformly; then heating to 80 ℃, and preserving the heat for 3 hours to obtain a prepolymer; the prepolymer is sealed and stored for later use.

3) Uniformly mixing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, acetal resin, silicon nitride, ceramic powder, dibutyltin dilaurate, an organic silicon surfactant and an oxidizing agent 1076 at 45 ℃; heating to 80 deg.C, removing water under vacuum (relative vacuum degree of-0.09 Mpa), and keeping the temperature for 2 hr; then cooling to 40 ℃ and discharging to obtain a chain extender; and sealing and storing the obtained chain extender for later use.

4) Rapidly and uniformly mixing the prepolymer and the chain extender at a stirring speed of 3000r/m at the temperature of 40 ℃; then injecting into a mold at 90 ℃, heating to 115 ℃, curing for 24h, and curing at 105 ℃ for 6h to obtain a finished product.

Example 5

Wherein, the prepolymerization raw material comprises 100Kg of polytetrahydrofuran ether glycol, 120Kg of diphenylmethane diisocyanate and 2Kg of triethanolamine.

The chain extension raw materials comprise 22Kg of 1, 4-butanediol, 8Kg of acetal resin, 8Kg of silicon nitride, 5Kg of ceramic powder, 0.4Kg of triethylene diamine, 1Kg of silicone surfactant and 4Kg of oxidant 1010.

The embodiment of the application also discloses a preparation method of the high-hardness polyurethane composite material, which comprises the following steps:

1) weighing the following components in proportion: 100Kg of polytetrahydrofuran ether glycol, 120Kg of diphenylmethane diisocyanate, 2Kg of triethanolamine, 22Kg of 1, 4-butanediol, 8Kg of acetal resin, 8Kg of silicon nitride, 5Kg of ceramic powder, 0.4Kg of triethylene diamine, 1Kg of organosilicon surfactant and 10104 Kg of oxidant.

2) Respectively heating polytetrahydrofuran ether glycol, diphenylmethane diisocyanate and triethanolamine to 110 deg.C, vacuumizing for vacuum dehydration for 2h (relative vacuum degree of-0.09 Mpa), and cooling to room temperature; dripping the dehydrated diphenylmethane diisocyanate into the dehydrated polytetrahydrofuran ether glycol at room temperature under the protection of nitrogen, and stirring to make the mixture uniform, wherein the dripping time is controlled to be 2 hours; adding triethanolamine after the dropwise addition is finished and stirring uniformly; then heating to 75 ℃, and preserving the heat for 3 hours to obtain a prepolymer; the prepolymer is sealed and stored for later use.

3) Uniformly mixing 1, 4-butanediol, acetal resin, silicon nitride, ceramic powder, triethylene diamine, an organosilicon surfactant and an oxidant 1010 at 40 ℃; heating to 75 deg.C, removing water under vacuum (relative vacuum degree of-0.09 Mpa), and maintaining the temperature for 3 hr; then cooling to 40 ℃ and discharging to obtain a chain extender; and sealing and storing the obtained chain extender for later use.

4) Rapidly and uniformly mixing the prepolymer and the chain extender at a stirring speed of 2000r/m at the temperature of 40 ℃; then injecting into a mold at 90 ℃, heating to 125 ℃, curing for 16h, and curing at 105 ℃ for 7h to obtain a finished product.

Example 6

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, diphenylmethane diisocyanate in a prepolymerization raw material is replaced by 3,3' -dimethyl biphenyl-4, 4-diisocyanate.

The method specifically comprises the following steps: the prepolymerization raw material comprises 100Kg of polypropylene carbonate glycol, 110Kg of 3,3' -dimethyl biphenyl-4, 4-diisocyanate and 2Kg of triethanolamine.

Example 7

The method specifically comprises the following steps: the prepolymerization raw material comprises 100Kg of polypropylene carbonate glycol, 110Kg of p-phenylene diisocyanate and 2Kg of triethanolamine.

Example 8

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the pre-polymerization raw material does not contain triethanolamine.

The method specifically comprises the following steps: the prepolymerization raw material comprises 100Kg of polypropylene carbonate glycol and 110Kg of diphenylmethane diisocyanate.

Example 9

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the prepolymerization raw material contains 1Kg of triethanolamine.

The method specifically comprises the following steps: the prepolymerization raw material comprises 100Kg of polypropylene carbonate glycol, 110Kg of diphenylmethane diisocyanate and 1Kg of triethanolamine.

Example 10

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the prepolymerization raw material contains 3Kg of triethanolamine.

Example 11

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the prepolymerization raw material contains 4Kg of triethanolamine.

Example 12

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the chain extension raw material does not contain acetal resin.

The method specifically comprises the following steps: the chain extension raw materials comprise 22Kg of 1, 4-butanediol, 6Kg of silicon nitride, 7Kg of ceramic powder, 0.3Kg of triethylene diamine, 0.8Kg of organosilicon surfactant and 3Kg of oxidant 1010.

Example 13

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the chain extension raw material contains 3Kg of acetal resin.

The method specifically comprises the following steps: the chain extension raw materials comprise 22Kg of 1, 4-butanediol, 3Kg of acetal resin, 6Kg of silicon nitride, 7Kg of ceramic powder, 0.3Kg of triethylene diamine, 0.8Kg of organosilicon surfactant and 3Kg of oxidant 1010.

Example 14

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the chain extension raw material contains 6Kg of acetal resin.

The method specifically comprises the following steps: the chain extension raw materials comprise 22Kg of 1, 4-butanediol, 6Kg of acetal resin, 6Kg of silicon nitride, 7Kg of ceramic powder, 0.3Kg of triethylene diamine, 0.8Kg of organosilicon surfactant and 3Kg of oxidant 1010.

Example 15

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the chain extension raw material contains 12Kg of acetal resin.

The method specifically comprises the following steps: the chain extension raw materials comprise 22Kg of 1, 4-butanediol, 12Kg of acetal resin, 6Kg of silicon nitride, 7Kg of ceramic powder, 0.3Kg of triethylene diamine, 0.8Kg of organosilicon surfactant and 3Kg of oxidant 1010.

Example 16

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the chain extension raw material contains 15Kg of acetal resin.

The method specifically comprises the following steps: the chain extension raw materials comprise 22Kg of 1, 4-butanediol, 15Kg of acetal resin, 6Kg of silicon nitride, 7Kg of ceramic powder, 0.3Kg of triethylene diamine, 0.8Kg of organosilicon surfactant and 3Kg of oxidant 1010.

Example 17

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the chain extension raw material does not contain silicon nitride.

The method specifically comprises the following steps: the chain extension raw materials comprise 22Kg of 1, 4-butanediol, 10Kg of acetal resin, 7Kg of ceramic powder, 0.3Kg of triethylene diamine, 0.8Kg of organosilicon surfactant and 3Kg of oxidant 1010.

Example 18

This embodiment is substantially the same as embodiment 1 except that: in the high-hardness polyurethane composite material, the chain extension raw material does not contain ceramic powder.

The method specifically comprises the following steps: the chain extension raw materials comprise 22Kg of 1, 4-butanediol, 10Kg of acetal resin, 6Kg of silicon nitride, 0.3Kg of triethylene diamine, 0.8Kg of organosilicon surfactant and 3Kg of oxidant 1010.

Comparative example 1

This comparative example is essentially the same as example 1, except that: in the preparation method of the high-hardness polyurethane composite material, in the step (2), the polypropylene carbonate glycol, the diphenylmethane diisocyanate and the triethanolamine are not dehydrated; in the step (3), the 1, 4-butanediol, acetal resin, silicon nitride, ceramic powder, triethylene diamine, an organosilicon surfactant and the oxidant 1010 are not dehydrated.

The method comprises the following specific steps:

2) At room temperature and under the protection of nitrogen, dripping diphenylmethane diisocyanate into the polypropylene carbonate glycol and stirring to make the mixture uniform, wherein the dripping time is controlled to be 2 hours; adding triethanolamine after the dropwise addition is finished and stirring uniformly; then heating to 85 ℃, and preserving the heat for 3 hours to obtain a prepolymer; the prepolymer is sealed and stored for later use.

3) Uniformly mixing 1, 4-butanediol, acetal resin, silicon nitride, ceramic powder, triethylene diamine, an organosilicon surfactant and an oxidant 1010 at 40 ℃; heating to 80 ℃ and then preserving heat for 3 h; then cooling to 35 ℃ and discharging to obtain a chain extender; and sealing and storing the obtained chain extender for later use.

Comparative example 2

The method comprises the following specific steps:

2) Respectively heating the polypropylene carbonate glycol, the diphenylmethane diisocyanate and the triethanolamine to 110 ℃, vacuumizing, performing vacuum dehydration for 3h (the relative vacuum degree is-0.09 Mpa), and then cooling to room temperature for later use; at room temperature, dripping the dehydrated diphenylmethane diisocyanate into the dehydrated polypropylene carbonate glycol, and stirring to make the mixture uniform, wherein the dripping time is controlled to be 2 hours; adding triethanolamine after the dropwise addition is finished and stirring uniformly; then heating to 85 ℃, and preserving the heat for 3 hours to obtain a prepolymer; the prepolymer is sealed and stored for later use.

Performance detection

The polyurethane composites provided in examples 1-18 and comparative examples 1-2 were subjected to performance testing.

1. Shore hardness test: reference standard: GB/T531.2; sample size (length × width × height): 30mm × 30mm × 8 mm; the test force was maintained for 3 s.

2. And (3) testing tensile strength: reference standard: GB/T528; the sample is dumbbell-shaped (type 1); the moving speed of the clamp is 500 mm/min; the temperature during the experiment was 25 ℃.

3. 100% stress at definite elongation test: reference standard: ASTM D412; using test method a, the sample was dumbbell-shaped (type 1); the temperature during the experiment is 25 ℃, and the relative humidity during the experiment is 60%; the distance between the upper clamp and the lower clamp of the tensile machine is 80mm, and the separation speed of the sample chuck is 500 mm/min.

4. 300% stress at definite elongation test: reference standard: ASTM D412; using test method a, the test specimens were dumbbell-shaped (type 1); the temperature during the experiment is 25 ℃, and the relative humidity during the experiment is 60%; the distance between the upper clamp and the lower clamp of the tensile machine is 80mm, and the separation speed of the sample chuck is 500 mm/min.

5. DIN abrasion test: reference standard: GB/T9867; the sample is cylindrical, the diameter of the sample is 16mm, and the height of the sample is 8 mm; method a was used and standard reference gel No. 1 was used.

The detection results are shown in table 1:

TABLE 1 test of Properties of samples of examples 1 to 18 and comparative examples 1 to 2

Referring to Table 1, examples 1-7 examined the mechanical properties of polyurethane composites made with different formulations. As can be seen from the detection results: the shore hardness of the polyurethane composite samples provided in examples 1-7 was above 89A, indicating that each sample had a higher hardness; at the same time, DIN abrasion of each sample was 55mm³The following also show thatWear resistance of (2).

Example 1 and examples 8 to 11 investigate the influence of the cross-linking agent triethanolamine on the mechanical properties of polyurethane composites; the comparison results can show that: when the triethanolamine is not added, the hardness of the finally prepared polyurethane material is 82A; with the increase of the adding amount of the triethanolamine, the Shore hardness of the prepared polyurethane material is higher and higher, and other mechanical properties are basically improved correspondingly; the triethanolamine has a positive effect on improving the mechanical property of the polyurethane material, and the triethanolamine serving as a cross-linking agent can improve the cross-linking degree of the prepared polyurethane material, so that the improvement of the mechanical strength and the hardness of the polyurethane material is facilitated. However, when the triethanolamine reaches 4Kg, the hardness and the mechanical strength of the prepared polyurethane are both reduced, because the viscosity of a polyurethane reaction system is increased due to the addition of an excessive amount of the cross-linking agent, the smooth synthesis of the polyurethane is influenced, and the mechanical properties of the polyurethane are influenced.

Example 1, examples 12-16 examined the influence of the addition of acetal resin on the mechanical properties of polyurethane composites; referring to the detection results, it can be found that: with the addition of acetal resin from 0 (example 12) to 12Kg (example 15), the hardness of the finally obtained polyurethane material is increased, and the mechanical strength and the wear resistance are correspondingly improved; the acetal resin has stronger hardness, and is mutually compatible with polyurethane after being added, so that the mechanical property of the acetal resin is improved. However, when the amount of acetal resin added reaches 15Kg (example 16), the hardness of the polyurethane is significantly reduced, and other mechanical properties are also reduced; this is because the addition of an excessive amount of acetal resin hinders the normal progress of the polyurethane synthesis reaction, thereby deteriorating the properties of polyurethane.

Example 17 investigates the influence of the addition of silicon nitride on the mechanical properties of polyurethane composites; in comparison with the test results of example 1, it can be found that: the addition of the silicon nitride is beneficial to improving the hardness and the wear resistance of the polyurethane material.

Example 18 investigates the influence of the addition of the ceramic powder on the mechanical properties of the polyurethane composite material; in comparison with the test results of example 1, it can be found that: similar to the action of silicon nitride, the ceramic powder is beneficial to improving the mechanical property of the polyurethane material.

Comparative example 1 investigates the influence of the raw materials not dehydrated during preparation on the mechanical properties of the final polyurethane finished product; compared with the result of the example 1, the detection result shows that the hardness of the polyurethane material prepared without dehydrating the raw materials is poor, and other mechanical properties are reduced; this is because isocyanate reacts with water to increase the viscosity of the prepolymer, which is not favorable for the smooth synthesis of polyurethane material and affects the performance of polyurethane material.

Comparative example 2 investigates the influence of the non-adoption of nitrogen protection on the mechanical property of the final polyurethane finished product when the diphenylmethane diisocyanate and the polypropylene carbonate glycol are mixed; see test results and compare the results of example 1: the mechanical properties of the prepared polyurethane material are reduced without nitrogen protection; the reason for this is that: the humidity in the air reacts with isocyanate, so that the viscosity of the prepolymer is increased, and the smooth synthesis of polyurethane is hindered.

The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.

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High-hardness polyurethane composite material and preparation method thereof

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