阅读说明：本技术 一种高耐热性的聚氨酯胶黏剂及其制备方法 (High-heat-resistance polyurethane adhesive and preparation method thereof ) 是由 范坤泉 于 2021-08-26 设计创作，主要内容包括：本发明涉及聚氨酯胶黏剂技术领域,具体地说,涉及一种高耐热性的聚氨酯胶黏剂及其制备方法。其包括以下原料组成：聚氨酯预聚体、共聚树脂、填充剂、耐热剂、溶剂、催化剂和分散剂；加入的耐热剂,由于磷添加剂的增加,使胶黏剂受热时能产生阻燃性的碳化层,通过加入填充剂可提升胶黏剂的强度,同时由于各种氧化物的添加使得胶黏剂的阻燃性也大大增加,并且填充剂中的金属氧化物与富含大量磷酸元素的耐热剂之间进行反应,生产具有酸化氧化磷产物,而产物可用于对共聚树脂进行酸化,生产磷酸改性的共聚树脂,该改性树脂与预聚体之间具有较好的融合力,进一步提升了胶黏剂的附着力和阻燃性。(The invention relates to the technical field of polyurethane adhesives, in particular to a high-heat-resistance polyurethane adhesive and a preparation method thereof. The feed comprises the following raw materials: polyurethane prepolymer, copolymer resin, filler, heat-resistant agent, solvent, catalyst and dispersant; the added heat-resistant agent can generate a flame-retardant carbonized layer when the adhesive is heated due to the addition of the phosphorus additive, the strength of the adhesive can be improved by adding the filler, meanwhile, the flame retardance of the adhesive is greatly increased due to the addition of various oxides, and the metal oxides in the filler and the heat-resistant agent rich in a large amount of phosphoric acid elements are reacted to produce an acidified phosphorus oxide product, and the product can be used for acidifying the copolymer resin to produce phosphoric acid modified copolymer resin, so that the modified resin has better fusion force with the prepolymer, and the adhesive force and the flame retardance of the adhesive are further improved.)

1. The polyurethane adhesive with high heat resistance is characterized by comprising the following raw materials: 130 parts of polyurethane prepolymer, 20-30 parts of copolymer resin, 12-17 parts of filler, 1-5 parts of heat-resistant agent, 30-50 parts of solvent, 0.1-3 parts of catalyst and 0.1-3 parts of dispersant;

the heat-resistant agent is selected from one or more of 2, 5-dihydroxyphenyl (diphenyl) phosphine oxide, diphenyl phosphorus oxide, ditolyl bis diphenyl phosphine oxide, pentaerythritol phosphate and triphenyl phosphate.

2. The high heat resistant polyurethane adhesive according to claim 1, wherein: the polyurethane prepolymer is synthesized by the reaction of butanediol adipate glycol and diisocyanate, wherein the molecular weight of the butanediol adipate glycol is 2000-6000 g/Pmol.

3. The high heat resistant polyurethane adhesive according to claim 1, wherein: the copolymer resin is selected from one or more of epoxy resin, acrylic resin, rosin resin, phenolic resin, terpene resin and petroleum resin.

4. The high heat resistant polyurethane adhesive according to claim 1, wherein: the filler is selected from a plurality of mixtures of alumina powder, mica powder, quartz powder, titanium dioxide powder, magnesium powder, silicon dioxide powder and ferric oxide powder.

5. The high heat resistant polyurethane adhesive according to claim 1, wherein: at least one of the solvents toluene, acetic acid, chlorobenzene and cyclohexanone.

6. The high heat resistant polyurethane adhesive according to claim 1, wherein: the catalyst is dibutyltin dilaurate.

7. The high heat resistant polyurethane adhesive according to claim 1, wherein: the dispersing agent is selected from one of ethylene-vinyl acetate and ethylene-acrylic acid.

8. A method for preparing the high heat-resistant polyurethane adhesive according to any one of claims 1 to 7, comprising the steps of;

s1, adding the polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;

s2, adding diisocyanate, stirring, adding a catalyst, and performing prepolymerization to obtain a polyurethane prepolymer;

s3, adding the polyurethane prepolymer, the copolymer resin, the filler, the heat-resistant agent and the dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder to perform extrusion molding to obtain granules;

and S4, adding the master batch into a solvent, and dissolving to obtain the polyurethane adhesive.

9. The method of preparing a polyurethane adhesive having high heat resistance as set forth in claim 8, wherein: in the S2, the temperature is 90-110 ℃, and the rotation speed is 200-220 r/min.

10. The method of preparing a polyurethane adhesive having high heat resistance as set forth in claim 8, wherein: in the S3, the heating temperature is 100-120 ℃, and the rotation speed is 500-600 r/min.

Technical Field

The invention relates to the technical field of polyurethane adhesives, in particular to a high-heat-resistance polyurethane adhesive and a preparation method thereof.

Background

The polyurethane adhesive is an important component in polyurethane resin which is rapidly developed at present, has excellent performance, is widely applied in many aspects, is one of eight important varieties of synthetic adhesives, has excellent shear strength and impact resistance, is suitable for various structural bonding fields, has excellent flexibility, has strong bonding force, and also has excellent buffering and damping functions, the low-temperature and ultralow-temperature performance of the polyurethane adhesive exceeds that of all other types of adhesives, and the thermoplastic polyurethane adhesive is a synthetic polyurethane adhesive made of thermoplastic polyurethane, is softened and bonded when being heated, and is hardened after being cooled to have certain strength.

The existing polyurethane adhesive has poor heat resistance, is very easy to melt at high temperature after being cured, and simultaneously, because the addition of chemicals in the adhesive is excessive, the melting point of the adhesive is reduced, and the flame retardance is reduced, so that the defect of the prior art is overcome by the high-heat-resistance polyurethane adhesive.

Disclosure of Invention

The present invention is directed to a polyurethane adhesive with high heat resistance and a preparation method thereof, so as to solve the problems mentioned in the background art.

In order to achieve the above object, in one aspect, the present invention provides a polyurethane adhesive with high heat resistance, which comprises the following raw materials: 130 parts of polyurethane prepolymer, 20-30 parts of copolymer resin, 12-17 parts of filler, 1-5 parts of heat-resistant agent, 30-50 parts of solvent, 0.1-3 parts of catalyst and 0.1-3 parts of dispersant;

the heat-resistant agent is one or more of 2, 5-dihydroxyphenyl (diphenyl) phosphine oxide, diphenyl phosphorus oxide, ditolyl bis diphenyl phosphine oxide, pentaerythritol phosphate and triphenyl phosphate, and is used for improving the heat resistance of the adhesive.

As a further improvement of the technical scheme, the polyurethane prepolymer is synthesized by the reaction of polybutylene glycol oxalate and diisocyanate, wherein the molecular weight of the polybutylene glycol oxalate is 2000-6000 g/Pmol.

As a further improvement of the technical scheme, the copolymer resin is selected from one or more of epoxy resin, acrylic resin, rosin resin, phenolic resin, terpene resin and petroleum resin, and can further increase the viscosity of the adhesive.

As a further improvement of the technical scheme, the filler is selected from a plurality of mixtures of alumina powder, mica powder, quartz powder, titanium dioxide powder, magnesium powder, silicon dioxide powder and ferric oxide powder, the strength of the adhesive can be improved by adding the filler, and meanwhile, the flame retardance of the adhesive is greatly increased due to the addition of various oxides.

As a further improvement of the technical scheme, the solvent is at least one of toluene, acetic acid, chlorobenzene and cyclohexanone.

As a further improvement of the technical scheme, the catalyst is dibutyltin dilaurate.

As a further improvement of the technical scheme, the dispersing agent is selected from one of ethylene-vinyl acetate and ethylene-acrylic acid.

In another aspect, the present invention provides a method for preparing a polyurethane adhesive having high heat resistance as described in any one of the above, comprising the steps of;

s1, adding the polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;

s2, adding diisocyanate, stirring, adding a catalyst, and performing prepolymerization to obtain a polyurethane prepolymer;

s3, adding the polyurethane prepolymer, the copolymer resin, the filler, the heat-resistant agent and the dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder to perform extrusion molding to obtain granules;

and S4, adding the master batch into a solvent, and dissolving to obtain the polyurethane adhesive.

Preferably, in S2, the temperature is 90-110 ℃, and the rotation speed is 200-220 r/min.

Preferably, in S3, the heating temperature is 100-120 ℃, and the rotation speed is 500-600 r/min.

In the invention, the metal oxide in the filler reacts with the heat-resistant agent rich in a large amount of phosphoric acid elements to produce an acidified phosphorus oxide product, the product can be used for acidifying the copolymer resin to produce phosphoric acid modified copolymer resin, the modified resin has better fusion force with the prepolymer, and the adhesive force and the flame retardance of the adhesive are further improved.

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

1. in the polyurethane adhesive with high heat resistance and the preparation method thereof, the added heat-resistant agent can generate a flame-retardant carbonized layer when the adhesive is heated due to the increase of the phosphorus additive.

2. According to the high-heat-resistance polyurethane adhesive and the preparation method thereof, the strength of the adhesive can be improved by adding the filler, meanwhile, the flame retardance of the adhesive is greatly increased due to the addition of various oxides, and the metal oxides in the filler react with the heat-resistant agent rich in a large amount of phosphoric acid elements to produce an acidified phosphorus oxide product, the product can be used for acidifying the copolymer resin to produce phosphoric acid modified copolymer resin, the modified resin and the prepolymer have good fusion force, and the adhesive force and the flame retardance of the adhesive are further improved.

Drawings

FIG. 1 is an overall flow diagram of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1 a polyurethane adhesive with high heat resistance and a method for preparing the same, comprising:

1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;

2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;

3. adding 130 parts of polyurethane prepolymer, 20 parts of copolymer resin, 12 parts of filler, 1 part of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;

4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.

Embodiment 2 a polyurethane adhesive with high heat resistance and a method for preparing the same, comprising:

1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;

2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;

3. adding 125 parts of polyurethane prepolymer, 22.5 parts of copolymer resin, 13 parts of filler, 2 parts of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;

4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.

Example 3 a polyurethane adhesive with high heat resistance and a method for preparing the same, comprising:

1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;

2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;

3. adding 120 parts of polyurethane prepolymer, 25 parts of copolymer resin, 15 parts of filler, 3 parts of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 120 ℃ and the rotating speed is 600 r/min;

4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.

Example 4 a polyurethane adhesive with high heat resistance and a method for preparing the same, comprising:

1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;

2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;

3. adding 15 parts of polyurethane prepolymer, 27.5 parts of copolymer resin, 16 parts of filler, 4 parts of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;

4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.

Example 5 a polyurethane adhesive with high heat resistance and a method for preparing the same, comprising:

1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;

2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;

3. adding 110 parts of polyurethane prepolymer, 30 parts of copolymer resin, 17 parts of filler, 5 parts of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;

4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.

In the adhesive, the heat-resistant agent is one or more selected from 2, 5-dihydroxyphenyl (diphenyl) phosphine oxide, diphenyl phosphorus oxide, ditolyl bis diphenyl phosphine oxide, pentaerythritol phosphate and triphenyl phosphate, and is used for improving the heat resistance of the adhesive;

the molecular weight of the polybutylene glycol oxalate glycol is 2000-6000 g/Pmol;

the copolymer resin is selected from one or more of epoxy resin, acrylic resin, rosin resin, phenolic resin, terpene resin and petroleum resin, and can further increase the viscosity of the adhesive; the filler is selected from a plurality of mixtures of alumina powder, mica powder, quartz powder, titanium dioxide powder, magnesium powder, silicon dioxide powder and ferric oxide powder, the strength of the adhesive can be improved by adding the filler, meanwhile, the flame retardance of the adhesive is greatly increased due to the addition of various oxides, and metal oxides in the filler react with a heat-resistant agent rich in a large amount of phosphoric acid elements to produce an acidified phosphorus oxide product which can be used for acidifying the copolymer resin to produce phosphoric acid modified copolymer resin, the modified resin has better fusion force with a prepolymer, and the adhesive force and the flame retardance of the adhesive are further improved;

at least one of solvents toluene, acetic acid, chlorobenzene and cyclohexanone;

the catalyst is dibutyltin dilaurate;

the dispersant is selected from one of ethylene-vinyl acetate and ethylene-acrylic acid.

The indexes of the polyurethane adhesive with high heat resistance in examples 1-5 of the present invention are specifically shown in table 1:

TABLE 1

As shown in Table 1, the high heat-resistant polyurethane adhesives prepared in examples 1-5 of the present invention all have good tensile strength and peel strength, and the heat distortion temperature is above 350 ℃, and the oxygen index also meets the flame retardant standard, so that the high heat-resistant polyurethane adhesives prepared in the present invention have good heat resistance and strength.

Comparative example 1 a polyurethane adhesive having high heat resistance and a method for preparing the same, comprising:

1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;

2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;

3. adding 120 parts of polyurethane prepolymer, 25 parts of copolymer resin, 15 parts of filler and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;

4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.

Comparative example 2 a polyurethane adhesive having high heat resistance and a method for preparing the same, comprising:

1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;

2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;

3. adding 120 parts of polyurethane prepolymer, 15 parts of filler, 3 parts of heat-resistant agent and 2 parts of dispersant into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;

4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.

Comparative example 3 a polyurethane adhesive having high heat resistance and a method for preparing the same, comprising:

1. adding polybutylene glycol oxalate into a reaction kettle, heating to 110 ℃ and 130 ℃, and performing vacuum dehydration;

2. then adding diisocyanate and stirring, and adding 0.1-3 parts of catalyst for prepolymerization to prepare a polyurethane prepolymer, wherein the temperature is 90-110 ℃, and the rotating speed is 200-220 r/min;

3. adding 120 parts of polyurethane prepolymer, 25 parts of copolymer resin, 3 parts of heat-resistant agent and 2 parts of dispersing agent into a reaction kettle, quickly stirring, performing vacuum defoaming, stopping stirring, and adding into an extruder for extrusion molding to obtain granules, wherein the heating temperature is 100-120 ℃, and the rotating speed is 500-600 r/min;

4. and adding the master batch into 40 parts of solvent, and dissolving to obtain the polyurethane adhesive.

The polyurethane adhesive with high heat resistance prepared by the invention has better heat resistance and strength, has a great relationship with the added heat-resistant agent, the added copolymer resin and the added filler, and in order to verify the related technical scheme, the applicant performs the following tests:

comparative examples 1 to 3: by adopting the method of example 3, the relevant indexes of the prepared adhesive are detected under the condition that the heat-resistant agent, the copolymer resin and the filler are removed, and the concrete indexes are shown in table 2:

TABLE 2

As shown in table 2, when the heat-resistant agent is removed, the thermal deformation temperature and the oxygen index of the adhesive decrease greatly, when the copolymer resin is removed, the peeling strength of the adhesive decreases greatly, and when the filler is removed, the tensile strength and the elongation at break of the adhesive decrease significantly, so that it can be shown that adding the heat-resistant agent, the copolymer resin and the filler in the adhesive production process is an important factor for changing the heat resistance and the strength of the adhesive.

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.