阅读说明：本技术 一种湿固化聚氨酯热熔胶及其制备方法 (Moisture-curing polyurethane hot melt adhesive and preparation method thereof ) 是由 刘向坤 王建斌 陈田安 解海华 于 2021-10-20 设计创作，主要内容包括：本发明公开了一种湿固化聚氨酯热熔胶,按重量百分比,包括以下组分：直链型聚酯多元醇20％～30％、聚醚多元醇20％～35％、聚碳酸酯多元醇20％-30％、抗氧剂0.1％～1％、异氰酸酯20％～25％、硅烷偶联剂1％～2％和催化剂0.05％～0.1％。本发明还公开了上述湿固化聚氨酯热熔胶的制备方法。本发明能够制得耐化学品的湿固化聚氨酯热熔胶。(The invention discloses a moisture-curing polyurethane hot melt adhesive which comprises the following components in percentage by weight: 20 to 30 percent of straight-chain polyester polyol, 20 to 35 percent of polyether polyol, 20 to 30 percent of polycarbonate polyol, 0.1 to 1 percent of antioxidant, 20 to 25 percent of isocyanate, 1 to 2 percent of silane coupling agent and 0.05 to 0.1 percent of catalyst. The invention also discloses a preparation method of the moisture-curing polyurethane hot melt adhesive. The invention can prepare the moisture-curing polyurethane hot melt adhesive resistant to chemicals.)

1. The moisture-curing polyurethane hot melt adhesive is characterized by comprising the following components in percentage by weight: 20 to 30 percent of straight-chain polyester polyol, 20 to 35 percent of polyether polyol, 20 to 30 percent of polycarbonate polyol, 0.1 to 1 percent of antioxidant, 20 to 25 percent of isocyanate, 1 to 2 percent of silane coupling agent and 0.05 to 0.1 percent of catalyst.

2. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the number average molecular weight of the linear polyester polyol is 3000-5000, and the linear polyester polyol is any one of polyethylene adipate glycol, polyhexamethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene terephthalate glycol, polybutylene terephthalate glycol and polytrimethylene terephthalate glycol.

3. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the polyether polyol has a number average molecular weight of 1000-4000, and is one or a combination of a polyoxypropylene glycol, a polyethylene glycol and a polytetrahydrofuran ether glycol.

4. The moisture-curing polyurethane hot melt adhesive of claim 1, wherein said polycarbonate polyol is Duraney G4672.

5. The moisture-curable polyurethane hot melt adhesive of claim 1, wherein said antioxidant is antioxidant 1010.

6. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the isocyanate is nicotineamwave MDI-100 and/or NDI produced by camanta new materials technology ltd.

7. The moisture-curing polyurethane hot melt adhesive of claim 1, wherein said catalyst is DMDEE.

8. The moisture-curable polyurethane hot melt adhesive according to claim 1, wherein the silane coupling agent is any one of KH-550, KH-560 and KH 570.

9. A method for preparing the moisture-curing polyurethane hot melt adhesive according to any one of claims 1 to 8, which is characterized by comprising the following steps:

(1) weighing the components in parts by weight, putting the polycarbonate polyol into a reaction kettle, stirring and mixing, heating to 140 ℃, vacuumizing, and dehydrating for 2.5 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(2) cooling the materials in the reaction kettle to 115 ℃, adding the molten isocyanate under the condition of high-speed stirring, starting heating equipment to heat the reaction kettle to 120 ℃, and keeping the vacuum degree of less than or equal to-0.095 MPa and stirring at 120 ℃ for 1-1.5h at high speed;

(3) after the reaction is finished, discharging the pressure of the reaction kettle by using high-purity nitrogen to obtain a prepolymer;

(4) putting the weighed straight-chain polyester polyol, polyether polyol and antioxidant into a reaction kettle, stirring and mixing, heating to 130-140 ℃, vacuumizing, and dehydrating for 2.5h under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(5) cooling the materials in the reaction kettle to 85 ℃, adding the melted prepolymer under the condition of high-speed stirring, continuing to react for 0.5h, adding the melted isocyanate, starting a heating device to heat the reaction kettle to 120 ℃, vacuumizing, and reacting for 1-1.5h under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(6) adding silane coupling agent, and stirring for 20min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(7) adding catalyst, and stirring for 15min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(8) and quickly discharging under the protection of nitrogen, packaging in an aluminum foil bag, and curing in an oven at 80-85 ℃ to obtain the moisture-curing polyurethane hot melt adhesive.

10. The process for preparing a moisture-curable polyurethane hot melt adhesive according to claim 9, wherein in step (2), the isocyanate is NDI, and in step (5), the isocyanate is MDI-100.

Technical Field

The invention relates to the field of hot melt adhesives, and particularly relates to a moisture-curable polyurethane hot melt adhesive and a preparation method thereof.

Background

Compared with the traditional hot melt adhesive, the wet curing polyurethane hot melt adhesive has the advantages of being high in bonding strength of the reactive adhesive, good in heat resistance and chemicals resistance and the like, and low in use temperature, and shows excellent bonding performance on wood, ceramics, fabrics, stones, metals, plastics, glass, rubber, leather and other base materials, so that the wet curing reactive polyurethane hot melt adhesive is widely applied to various industries, such as the automobile industry, the textile and clothing industry, the building industry, the electronic and electrical industry, the book manufacturing industry and the like, and is developed rapidly, and becomes one of the varieties of rapid adhesives developed in China.

With the rapid development of the electronic product industry, the demands of mobile phones and intelligent wearable products are continuously expanding. The application of the moisture-curing polyurethane hot melt adhesive in electronic products is increasing, mobile phones, earphones and other intelligent dresses need to be in contact with a human body for a long time in the using process, the human body can generate chemicals such as sweat, sebum, oleic acid and squalene, most of the moisture-curing polyurethane hot melt adhesives used in the existing mobile phones, earphones and other intelligent dressing industries have poor chemical resistance, the strength attenuation is too large after common chemicals such as the sebum, the oleic acid and the squalene are soaked, and even the adhesive failure is caused by the generation of adhesive failure. Therefore, how to solve the problem that the performance of the moisture-cured polyurethane is poor in resistance to various chemicals becomes a problem which needs to be solved urgently.

Disclosure of Invention

The invention aims to solve the technical problems that the existing moisture-curing polyurethane hot melt adhesive has poor chemical resistance and performance is reduced after being soaked by chemicals. The invention provides a moisture-curing polyurethane hot melt adhesive and a preparation method thereof, which can resist chemical corrosion, and the properties such as strength and the like are not obviously reduced after being soaked by chemicals.

In order to solve the technical problems, the embodiment of the invention discloses a moisture-curing polyurethane hot melt adhesive which comprises the following components in percentage by weight: 20 to 30 percent of straight-chain polyester polyol, 20 to 35 percent of polyether polyol, 20 to 30 percent of polycarbonate polyol, 0.1 to 1 percent of antioxidant, 20 to 25 percent of isocyanate, 1 to 2 percent of silane coupling agent and 0.05 to 0.1 percent of catalyst.

According to another specific embodiment, the embodiment of the invention discloses a moisture-curing polyurethane hot melt adhesive, wherein the number average molecular weight of a linear polyester polyol is 3000-5000, and the linear polyester polyol is any one of polyethylene glycol adipate glycol, polyhexamethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene terephthalate glycol, polybutylene terephthalate glycol and polypropylene terephthalate glycol.

According to another specific embodiment, the embodiment of the invention discloses a moisture-curing polyurethane hot melt adhesive, the number average molecular weight of the polyether polyol is 1000-4000, and the polyether polyol is one or more of polypropylene oxide glycol, polyethylene glycol and polytetrahydrofuran ether glycol.

According to another specific embodiment, the embodiment of the invention discloses a moisture-curing polyurethane hot melt adhesive, and the polycarbonate polyol is Duanle G4672.

According to another specific embodiment of the invention, the embodiment of the invention discloses a moisture-curing polyurethane hot melt adhesive, and the antioxidant is antioxidant 1010.

According to another embodiment of the invention, the embodiment of the invention discloses a moisture-curing polyurethane hot melt adhesive, and the isocyanate is NDI produced by Nicotiana Wanhua MDI-100 and/or Jiashan Bister New materials science and technology Limited in Zhejiang province.

According to another specific embodiment of the invention, the embodiment of the invention discloses a moisture-curing polyurethane hot melt adhesive, and the catalyst is DMDEE.

According to another specific embodiment of the invention, the embodiment of the invention discloses a moisture-curing polyurethane hot melt adhesive, and the silane coupling agent is any one of KH-550, KH-560 and KH 570.

The embodiment of the invention also discloses a preparation method of the moisture-curing polyurethane hot melt adhesive, which comprises the following steps:

(1) weighing the components according to the weight percentage, putting the polycarbonate polyol into a reaction kettle, stirring and mixing, heating to 140 ℃, vacuumizing, and dehydrating for 2.5 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(2) cooling the materials in the reaction kettle to 115 ℃, adding the molten isocyanate under the condition of high-speed stirring, starting heating equipment to heat the reaction kettle to 120 ℃, and keeping the vacuum degree of less than or equal to-0.095 MPa and stirring at 120 ℃ for 1-1.5h at high speed;

(3) after the reaction is finished, discharging the pressure of the reaction kettle by using high-purity nitrogen to obtain a prepolymer;

(4) putting the weighed straight-chain polyester polyol, polyether polyol and antioxidant into a reaction kettle, stirring and mixing, heating to 130-140 ℃, vacuumizing, and dehydrating for 2.5h under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(5) cooling the materials in the reaction kettle to 85 ℃, adding the melted prepolymer under the condition of high-speed stirring, continuing to react for 0.5h, adding the melted isocyanate, starting a heating device to heat the reaction kettle to 120 ℃, vacuumizing, and reacting for 1-1.5h under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(6) adding silane coupling agent, and stirring for 20min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(7) adding catalyst, and stirring for 15min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(8) and quickly discharging under the protection of nitrogen, packaging in an aluminum foil bag, and curing in an oven at 80-85 ℃ to obtain the moisture-curing polyurethane hot melt adhesive.

According to another embodiment of the present invention, the embodiment of the present invention discloses a method for preparing moisture-curable polyurethane hot melt adhesive, wherein in the step (2), the isocyanate is NDI, and in the step (5), the isocyanate is MDI-100.

The invention has the beneficial effects that: the invention adopts straight-chain polyester polyol, polycarbonate polyol and polyether polyol as the base materials of the moisture-curing polyurethane hot melt adhesive, and has better bonding strength; meanwhile, the system is modified by the silane coupling agent, so that the obtained moisture-curing polyurethane hot melt adhesive can still keep higher bonding strength after being soaked by chemicals such as sweat, oleic acid, sebum, squalene and the like, and is suitable for electronic consumer goods such as intelligent wearing, mobile phones, flat plates and the like.

Detailed Description

The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure. While the invention will be described in conjunction with the preferred embodiments, it is not intended that features of the invention be limited to these embodiments. On the contrary, the invention is described in connection with the embodiments for the purpose of covering alternatives or modifications that may be extended based on the claims of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be practiced without these particulars. Moreover, some of the specific details have been left out of the description in order to avoid obscuring or obscuring the focus of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.

Example 1

The raw materials used in example 1 are in parts by weight as follows:

25 parts of straight-chain polyester polyol,

30 parts of polyether polyol,

20 parts of polycarbonate polyol, namely 20 parts of polycarbonate polyol,

0.5 part of antioxidant 1010 is added,

the NDI is 5 parts by weight,

the MDI-100 is 20 parts by weight,

1 part of a silane coupling agent, namely,

0.1 part of catalyst;

the method of preparing the moisture-curable polyurethane hot melt adhesive of example 1, comprising the steps of:

(1) weighing the components in parts by weight, putting polycarbonate polyol into a reaction kettle, stirring and mixing, heating to 138 ℃, vacuumizing, and dehydrating for 2.5 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(2) cooling the materials in the reaction kettle to 115 ℃, adding the melted NDI under the condition of high-speed stirring, starting a heating device to heat the reaction kettle to 120 ℃, and keeping the vacuum degree to be less than or equal to-0.095 MPa, and stirring at 120 ℃ for 1.5h at a high speed;

(3) after the reaction is finished, discharging the pressure of the reaction kettle by using high-purity nitrogen to obtain a prepolymer for later use;

(4) putting the straight-chain polyester polyol, the polyether polyol and the antioxidant weighed in the step (1) into a reaction kettle, stirring and mixing, heating to 138 ℃, vacuumizing, and dehydrating for 2.5 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(5) cooling the materials in the reaction kettle to 85 ℃, adding the melted prepolymer obtained in the step (3) under the condition of high-speed stirring, continuing to react for 0.5h, adding melted MDI-100, starting a heating device to heat the reaction kettle to 120 ℃, vacuumizing, and reacting for 1.5h under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(6) adding silane coupling agent, and stirring for 20min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(7) adding catalyst, and stirring for 15min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(8) and quickly discharging under the protection of nitrogen, packaging in an aluminum foil bag, and curing in an oven at 80-85 ℃ to obtain the moisture-curing polyurethane hot melt adhesive.

Example 2

The weight parts of the raw materials used in example 2 are as follows:

25 parts of straight-chain polyester polyol,

25 parts of polyether glycol,

25 parts of polycarbonate polyol, namely 25 parts of polycarbonate polyol,

0.5 part of antioxidant 1010 is added,

the NDI is 7 parts by weight,

the MDI-100 is 18 parts by weight,

1 part of a silane coupling agent, namely,

0.1 part of catalyst;

the method of preparing the moisture-curable polyurethane hot melt adhesive of example 2 comprises the steps of:

(1) weighing the components in parts by weight, putting polycarbonate polyol into a reaction kettle, stirring and mixing, heating to 138 ℃, vacuumizing, and dehydrating for 2.5 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(2) cooling the materials in the reaction kettle to 115 ℃, adding the melted NDI under the condition of high-speed stirring, starting a heating device to heat the reaction kettle to 120 ℃, and keeping the vacuum degree to be less than or equal to-0.095 MPa, and stirring at 120 ℃ for 1.5h at a high speed;

(3) after the reaction is finished, discharging the pressure of the reaction kettle by using high-purity nitrogen to obtain a prepolymer for later use;

(4) putting the straight-chain polyester polyol, the polyether polyol and the antioxidant weighed in the step (1) into a reaction kettle, stirring and mixing, heating to 138 ℃, vacuumizing, and dehydrating for 2.5 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(5) cooling the materials in the reaction kettle to 85 ℃, adding the melted prepolymer obtained in the step (3) under the condition of high-speed stirring, continuing to react for 0.5h, adding melted MDI-100, starting a heating device to heat the reaction kettle to 120 ℃, vacuumizing, and reacting for 1.5h under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(6) adding silane coupling agent, and stirring for 20min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(7) adding catalyst, and stirring for 15min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(8) and quickly discharging under the protection of nitrogen, packaging in an aluminum foil bag, and curing in an oven at 80-85 ℃ to obtain the moisture-curing polyurethane hot melt adhesive.

Example 3

The weight parts of the raw materials used in example 3 are as follows:

25 parts of straight-chain polyester polyol,

20 parts of polyether glycol,

30 parts of polycarbonate polyol,

0.5 part of antioxidant 1010 is added,

the NDI is 9 parts by weight,

the MDI-100 is 16 parts by weight,

1 part of a silane coupling agent, namely,

0.1 part of catalyst;

the method of preparing the moisture-curable polyurethane hot melt adhesive of example 3, comprising the steps of:

(1) weighing the components in parts by weight, putting polycarbonate polyol into a reaction kettle, stirring and mixing, heating to 138 ℃, vacuumizing, and dehydrating for 2.5 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(2) cooling the materials in the reaction kettle to 115 ℃, adding the melted NDI under the condition of high-speed stirring, starting a heating device to heat the reaction kettle to 120 ℃, and keeping the vacuum degree to be less than or equal to-0.095 MPa, and stirring at 120 ℃ for 1.5h at a high speed;

(3) after the reaction is finished, discharging the pressure of the reaction kettle by using high-purity nitrogen to obtain a prepolymer for later use;

(4) putting the straight-chain polyester polyol, the polyether polyol and the antioxidant weighed in the step (1) into a reaction kettle, stirring and mixing, heating to 138 ℃, vacuumizing, and dehydrating for 2.5 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(5) cooling the materials in the reaction kettle to 85 ℃, adding the melted prepolymer obtained in the step (3) under the condition of high-speed stirring, continuing to react for 0.5h, adding melted MDI-100, starting a heating device to heat the reaction kettle to 120 ℃, vacuumizing, and reacting for 1.5h under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(6) adding silane coupling agent, and stirring for 20min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(7) adding catalyst, and stirring for 15min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(8) and quickly discharging under the protection of nitrogen, packaging in an aluminum foil bag, and curing in an oven at 80-85 ℃ to obtain the moisture-curing polyurethane hot melt adhesive.

Comparative example:

the polyurethane hot melt adhesive D1 of the comparative example comprises the following raw materials in parts by weight:

27 parts of straight-chain polyester polyol,

35 parts of polyether polyol, namely 35 parts of polyether polyol,

0.5 part of antioxidant 1010 is added,

the MDI-100 is 25 parts by weight,

0.1 part of catalyst;

the preparation method of the moisture-curing polyurethane hot melt adhesive D1 comprises the following steps:

(1) weighing the straight-chain polyester polyol, the polyether polyol and the antioxidant which are weighed according to the weight parts, putting the straight-chain polyester polyol, the polyether polyol and the antioxidant into a reaction kettle, stirring and mixing, heating to 138 ℃, vacuumizing, and dehydrating for 2.5 hours under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(2) cooling the materials in the reaction kettle to 85 ℃, adding melted MDI-100 under the condition of high-speed stirring, simultaneously starting heating equipment to heat the reaction kettle to 120 ℃, vacuumizing, and reacting for 1.5h under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(3) adding catalyst, and stirring for 35min under the condition that the vacuum degree is less than or equal to-0.095 MPa;

(4) and quickly discharging under the protection of nitrogen, packaging in an aluminum foil bag, and curing in an oven at 80-85 ℃ to obtain the moisture-curing polyurethane hot melt adhesive.

The moisture-curing polyurethane hot melt adhesives prepared in examples 1 to 3 were subjected to a relevant performance test with moisture-curing polyurethane hot melt adhesive D1 in the prior art, and the specific performance test results are shown in Table 1. Wherein, the viscosity test standard refers to GB/T2794.

Table 1 examples 1-3 and comparative examples performance test results

As can be seen from the table 1, compared with the polyurethane hot melt adhesive in the prior art, the moisture-curable polyurethane hot melt adhesive prepared by the method has good performances of chemicals such as oil acid resistance, squalene resistance and sebum resistance, and the drawing strength can still meet the requirements even if the moisture-curable polyurethane hot melt adhesive is soaked in the chemicals such as oleic acid, squalene resistance and sebum resistance for 48 hours.

While the invention has been described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a more particular description of the invention than is possible with reference to the specific embodiments, which are not to be construed as limiting the invention. Various changes in form and detail, including simple deductions or substitutions, may be made by those skilled in the art without departing from the spirit and scope of the invention.