Reactive polyurethane hot melt adhesive containing self-made flame-retardant polyester polyol

Abstract

The invention provides a reactive polyurethane hot melt adhesive containing self-made flame-retardant polyester polyol. The polyurethane hot melt adhesive is prepared by the following steps: mixing flame-retardant polyester polyol with common polyester polyol and polyether polyol in vacuum at 110 DEG C, dehydrating in a stirring reaction kettle for 60 minutes, cooling to 75 DEG C, adding 4, 4 '-diphenyl methyl diisocyanate into the mixture, reacting in nitrogen for 60 minutes, and reacting in vacuum at 100 DEG C for 60 minutes. The flame-retardant polyester polyol is prepared by carrying out polymerization reaction on vinyl ethyl phosphate, vinyl isobutyl phosphate, 1, 6-hexanediol and 1, 4-butanediol under the action of a catalyst. The reaction type polyurethane hot melt adhesive containing the self-made flame-retardant polyester polyol can meet the flame retardant property UL94-V0, the viscosity (90 DEG C) is 3000-4500 mpa.s, and the flame-retardant reaction type polyurethane hot melt adhesive does not contain halogen.

Description

Technical Field

[0001] The invention relates to the technical field of hot melt adhesives, in particular to a reactive polyurethane hot melt adhesive containing self-made flame retardant polyester polyol. Background Art

[0002] Hot melt adhesive is a plastic adhesive. Its physical state changes with temperature within a certain temperature range, but its chemical properties remain unchanged. It is non-toxic and tasteless, and is an environmentally friendly chemical product. It is popular because the product itself is solid, easy to package, transport, store, solvent-free, pollution-free, non-toxic; and has the advantages of simple production process, high added value, high bonding strength, and fast speed. It is solid at room temperature, and becomes a liquid that can flow and has a certain viscosity when heated and melted to a certain temperature.

[0003] With the in-depth development of firefighting, mining, electricity and other industries, more and more industries have high requirements for the flame retardant properties of textiles used in human clothing. Therefore, there is a strong demand for the research and development of flame retardant reactive polyurethane hot melt adhesives for textile composites.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a reactive polyurethane hot melt adhesive containing self-made flame retardant polyester polyol.

[0006] To achieve the above object, the present invention provides the following technical solutions: A reactive polyurethane hot melt adhesive containing self-made flame-retardant polyester polyol, wherein the polyurethane hot melt adhesive is prepared by mixing the flame-retardant polyester polyol with common polyester polyol and polyether polyol under vacuum at 110°C, dehydrating the mixture in a stirred reactor for 60 minutes, lowering the temperature to 75°C, adding 4,4'-2,4'-diphenylmethyl diisocyanate to the mixture, reacting the mixture in nitrogen for 60 minutes, and then reacting the mixture under vacuum at 100°C for 60 minutes; the flame-retardant polyester polyol comprises vinyl ethyl phosphate, vinyl isobutyl phosphate, 1,6-hexanediol and 1,4-butanediol, and is prepared by polymerization reaction under the action of a catalyst.

[0007] Furthermore, the weight percentages of the vinyl ethyl phosphate, vinyl isobutyl phosphate, 1,6-hexanediol and 1,4-butanediol are calculated as 0%-40% vinyl ethyl phosphate, 0%-70% vinyl isobutyl phosphate, 0%-40% 1,6-hexanediol and 0%-60% 1,4-butanediol, respectively.

[0008] Furthermore, the flame retardant polyester polyol polymerization method is carried out in a stirred atmospheric pressure autoclave, the stirring time is 12-96 hours, and the polymerization temperature is 150-300°C.

[0009] Furthermore, the flame retardant polyester polyol has a molecular weight of 1000-4000 g / mol.

[0010] Furthermore, the preparation method of the flame-retardant polyester polyol is as follows: the vinyl ethyl phosphate, vinyl isobutyl phosphate, 1,6-hexanediol, 1,4-butanediol, and the catalyst are stirred and dehydrated at 110-200° C. for 1-4 hours, then the temperature is raised to 210-270° C., and vacuum is applied until the vacuum degree is below -0.099 MPa, and then the temperature is set to 210-280° C. for ester exchange reaction until the hydroxyl value is 26-116 mgKOH / g, the reaction is terminated, and the pressure and temperature are reduced to discharge the material.

[0011] The present invention also discloses a method for preparing the polyurethane hot melt adhesive, comprising the following steps: Stir and dehydrate vinyl ethyl phosphate, vinyl isobutyl phosphate, 1,6-hexanediol, 1,4-butanediol and a catalyst at 110-200° C. for 1-4 hours, then heat to 210-270° C., evacuate until the vacuum degree is below -0.099 MPa, then set the temperature to 210-280° C. for transesterification reaction until the hydroxyl value is 26-116 mgKOH / g, terminate the reaction, reduce pressure and temperature, and obtain a flame-retardant polyester polyol; The flame retardant polyester polyol was mixed with ordinary polyester polyol and polyether polyol under vacuum at 110°C and then dehydrated in a stirred reactor for 60 minutes, and then the temperature was lowered to 75°C; A certain amount of 4,4'-2,4'-diphenylmethyl diisocyanate was added to the mixture, and the mixture was reacted in nitrogen for 60 minutes, and then in vacuum at about 100°C for 60 minutes.

[0012] The invention also discloses a processed product obtained by using the polyurethane hot melt adhesive.

[0013] Compared with the prior art, the beneficial effects of the present invention are: the reactive polyurethane hot melt adhesive containing homemade flame-retardant polyester polyol can meet the flame retardant performance UL94-V0, the viscosity (90°C) is 3000-4500mpa.s, and the flame-retardant reactive polyurethane hot melt adhesive does not contain halogen. DETAILED DESCRIPTION

[0014] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0015] Example 1 This embodiment provides a reactive polyurethane hot melt adhesive containing homemade flame retardant polyester polyol.

[0016] The flame-retardant polyester polyol was prepared by the following method: 40 g of vinyl ethyl phosphate, 30 g of 1,6-hexanediol and 0.003 g of a homemade catalyst were introduced into a stirred atmospheric pressure reactor in sequence, stirring was turned on, the temperature was set to 160° C. for 1 h for dehydration, the temperature was raised to 220° C. for 24 h and then restored to atmospheric pressure, small molecular monomers were removed through a distillation tower, the temperature was lowered to 130° C., the material was discharged and stored, and a flame-retardant polyester polyol A with a molecular weight of 1500 g / mol was obtained.

[0017] The method for preparing a flame retardant reactive polyurethane hot melt adhesive by mixing flame retardant polyester polyol A with different common polyester polyols and polyether polyols is as follows: a certain amount of polyol is dehydrated in a stirred reactor under vacuum at a temperature of 110°C for about 60 minutes, and then the temperature is reduced to 75°C, a certain amount of 4,4'-2,4'-diphenylmethyl diisocyanate (pure MDI) is added to the mixture, and the mixture is reacted in a nitrogen atmosphere for 60 minutes, and then reacted at a vacuum of about 100°C for 60 minutes. After the reaction, the hot melt adhesive is loaded into a dry container made of aluminum, tin or its composite film.

[0018] Example 2 This embodiment provides a reactive polyurethane hot melt adhesive containing homemade flame retardant polyester polyol.

[0019] The flame-retardant polyester polyol was prepared by the following method: 35 g of vinyl isobutyl phosphate, 37.5 g of 1,4-butanediol and 0.004 g of a homemade catalyst were introduced into a stirred atmospheric pressure reactor in sequence, stirring was turned on, the temperature was set to 150° C. for 1.5 h of dehydration, the temperature was raised to 210° C. for 48 h and then restored to atmospheric pressure, small molecular monomers were removed through a distillation tower, the temperature was lowered to 140° C., the material was discharged and stored, and a flame-retardant polyester polyol B with a molecular weight of 2000 g / mol was obtained.

[0020] The method for preparing a flame retardant reactive polyurethane hot melt adhesive by mixing the flame retardant polyester polyol B with different common polyester polyols and polyether polyols is as follows: a certain amount of polyol is dehydrated in a stirred reactor under vacuum at a temperature of 110°C for about 60 minutes, and then the temperature is reduced to 75°C, a certain amount of 4,4'-2,4'-diphenylmethyl diisocyanate (pure MDI) is added to the mixture, and the mixture is reacted in a nitrogen atmosphere for 60 minutes, and then reacted at a vacuum of about 100°C for 60 minutes. After the reaction is completed, the hot melt adhesive is loaded into a dry container made of aluminum, tin or its composite film.

[0021] Example 3 This embodiment provides a reactive polyurethane hot melt adhesive containing homemade flame retardant polyester polyol.

[0022] The flame-retardant polyester polyol was prepared by the following method: 10 g of vinyl ethyl phosphate, 28 g of vinyl isobutyl phosphate, 43 g of 1,6-hexanediol and 0.0035 g of a homemade catalyst were introduced into a stirred atmospheric pressure reactor in sequence, stirring was turned on, the temperature was set to 155° C. for 1 h for dehydration, the temperature was raised to 190° C. for 54 h and then restored to atmospheric pressure, small molecular monomers were removed through a distillation tower, the temperature was lowered to 140° C., the material was discharged and stored, and a flame-retardant polyester polyol C with a molecular weight of 4000 g / mol was obtained.

[0023] The method for preparing a flame retardant reactive polyurethane hot melt adhesive by mixing the flame retardant polyester polyol C with different common polyester polyols and polyether polyols is as follows: a certain amount of polyol is dehydrated in a stirred reactor under vacuum at a temperature of 110°C for about 60 minutes, and then the temperature is reduced to 75°C, a certain amount of 4,4'-2,4'-diphenylmethyl diisocyanate (pure MDI) is added to the mixture, and the mixture is reacted in a nitrogen atmosphere for 60 minutes, and then reacted at a vacuum of about 100°C for 60 minutes. After the reaction, the hot melt adhesive is loaded into a dry container made of aluminum, tin or its composite film.

[0024] Example 4 This embodiment provides a reactive polyurethane hot melt adhesive containing homemade flame retardant polyester polyol.

[0025] The flame-retardant polyester polyol was prepared by the following method: 26 g of vinyl ethyl phosphate, 11 g of vinyl isobutyl phosphate, 35 g of 1,6-hexanediol, 5.5 g of 1,4-butanediol and 0.004 g of a homemade catalyst were introduced into a stirred atmospheric pressure reactor in sequence, stirring was turned on, the temperature was set to 170° C. for 2 h of dehydration, the temperature was raised to 230° C. for 48 h and then restored to atmospheric pressure, small molecular monomers were removed through a distillation tower, the temperature was lowered to 120° C., the material was discharged and stored, and a flame-retardant polyester polyol D with a molecular weight of 3500 g / mol was obtained.

[0026] The method for preparing a flame retardant reactive polyurethane hot melt adhesive by mixing the flame retardant polyester polyol D with different common polyester polyols and polyether polyols is as follows: a certain amount of polyol is dehydrated in a stirred reactor under vacuum at a temperature of 110°C for about 60 minutes, and then the temperature is reduced to 75°C, a certain amount of 4,4'-2,4'-diphenylmethyl diisocyanate (pure MDI) is added to the mixture, and the mixture is reacted in a nitrogen atmosphere for 60 minutes, and then reacted at a vacuum of about 100°C for 60 minutes. After the reaction, the hot melt adhesive is loaded into a dry container made of aluminum, tin or its composite film.

[0027] Example 5 This embodiment provides a reactive polyurethane hot melt adhesive containing homemade flame retardant polyester polyol.

[0028] The flame-retardant polyester polyol was prepared by the following method: 32 g of vinyl ethyl phosphate, 7 g of vinyl isobutyl phosphate, 33.5 g of 1,6-hexanediol and 0.005 g of a homemade catalyst were introduced into a stirred atmospheric pressure reactor in sequence, the stirring was turned on, the temperature was set to 190° C. for 2 h of dehydration, the temperature was raised to 245° C. for 70 h and then restored to atmospheric pressure, small molecular monomers were removed through a distillation tower, the temperature was lowered to 160° C., the material was discharged and stored, and a flame-retardant polyester polyol E with a molecular weight of 4000 g / mol was obtained.

[0029] The method for preparing a flame retardant reactive polyurethane hot melt adhesive by mixing the flame retardant polyester polyol E with different common polyester polyols and polyether polyols is as follows: a certain amount of polyol is dehydrated in a stirred reactor under vacuum at a temperature of 110°C for about 60 minutes, and then the temperature is reduced to 75°C, a certain amount of 4,4'-2,4'-diphenylmethyl diisocyanate (pure MDI) is added to the mixture, and the mixture is reacted in a nitrogen atmosphere for 60 minutes, and then reacted at a vacuum of about 100°C for 60 minutes. After the reaction, the hot melt adhesive is loaded into a dry container made of aluminum, tin or its composite film.

[0030] The hot melt adhesive is placed in a dry container made of aluminum, tin or their composite film, and the relevant data are as follows: Example 1 Example 2 Example 3 Example 4 Example 5 Flame retardant polyester polyol A 80 Flame retardant polyester polyol B 80 Flame retardant polyester polyol C 80 Flame retardant polyester polyol D 80 Flame retardant polyester polyol E 80 <![CDATA[LX-8210 ① ]]> 10 10 10 <![CDATA[LX-8215 ① ]]> 20 10 10 20 10 Pure MDI 32.4 25.2 17.1 19.4 17.1 Viscosity (90℃) 3100 4400 5100 4700 5200 <![CDATA[Flame retardancy ② > V2 V1 V1 V0 V1 <![CDATA[50D polyester laminated to 50D polyester (peel strength)]]> ③ > 17.2 27.4 16.4 24.9 19 ①Lexin Chemical Polyester Polyol; ②Tested according to UL 94 method; ③Test method: Polyester cloth width 25mm, peeling speed 300mm / min, unit: N.

[0031] It should be noted that the above description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention. In addition, the technical features involved in the various embodiments of the present invention described above can be combined with each other as long as they do not conflict with each other. In addition, the above are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work belong to the scope of protection of the present invention.

Claims

1. A reactive polyurethane hot melt adhesive containing self-made flame-retardant polyester polyol, characterized in that: The polyurethane hot melt adhesive is prepared by mixing a flame retardant polyester polyol with a common polyester polyol and a polyether polyol under vacuum at a temperature of 110° C., dehydrating the mixture in a stirred reactor for 60 minutes, then lowering the temperature to 75° C., adding 4,4'-diphenylmethyl diisocyanate to the mixture, reacting the mixture in nitrogen for 60 minutes, and then reacting the mixture under vacuum at 100° C. for 60 minutes; the flame retardant polyester polyol comprises vinyl ethyl phosphate, vinyl isobutyl phosphate, 1,6-hexanediol, and 1,4-butanediol, and is prepared by polymerization reaction under the action of a catalyst.

2. A reactive polyurethane hot melt adhesive containing self-made flame-retardant polyester polyol as claimed in claim 1, characterized in that: The weight percentages of the vinyl ethyl phosphate, vinyl isobutyl phosphate, 1,6-hexanediol and 1,4-butanediol are calculated as 0%-40% for vinyl ethyl phosphate, 0%-70% for vinyl isobutyl phosphate, 0%-40% for 1,6-hexanediol and 0%-60% for 1,4-butanediol respectively.

3. A reactive polyurethane hot melt adhesive layer containing self-made flame retardant polyester polyol as claimed in claim 1, characterized in that: The flame retardant polyester polyol polymerization method is carried out in a stirring atmospheric pressure kettle, the stirring time is 12-96 hours, and the polymerization temperature is 150-300°C.

4. A reactive polyurethane hot melt adhesive containing self-made flame-retardant polyester polyol as claimed in claim 1, characterized in that: The molecular weight of the flame retardant polyester polyol is 1000-4000 g / mol.

5. A reactive polyurethane hot melt adhesive containing self-made flame-retardant polyester polyol as claimed in claim 1, characterized in that: The preparation method of flame-retardant polyester polyol is as follows: the vinyl ethyl phosphate, vinyl isobutyl phosphate, 1,6-hexanediol, 1,4-butanediol and catalyst are stirred and dehydrated at 110-200° C. for 1-4 hours, then the temperature is raised to 210-270° C., and vacuum is drawn until the vacuum degree is below -0.099 MPa, and then the temperature is set to 210-280° C. for ester exchange reaction until the hydroxyl value is 26-116 mgKOH / g, the reaction is terminated, and the pressure and temperature are reduced to discharge the material.

6. A method for preparing the polyurethane hot melt adhesive according to any one of claims 1 to 5, characterized in that: The following steps are involved: Vinyl ethyl phosphate, vinyl isobutyl phosphate, 1,6-hexanediol, 1,4-butanediol and a catalyst are stirred and dehydrated at 110-200°C for 1-4 hours, then the temperature is raised to 210-270°C, and vacuum is applied until the vacuum degree is below -0.099 MPa, and then the temperature is set to 210-280°C for transesterification reaction until the hydroxyl value is 26-116 mgKOH / g, the reaction is terminated, and the pressure and temperature are reduced to obtain a flame-retardant polyester polyol; The flame retardant polyester polyol was mixed with ordinary polyester polyol and polyether polyol under vacuum at 110°C and then dehydrated in a stirred reactor for 60 minutes, and then the temperature was reduced to 75°C; 4,4'-2,4'-diphenylmethyl diisocyanate was added to the mixture and reacted in nitrogen for 60 minutes and then in vacuum at about 100°C for 60 minutes.

7. A processed product obtained by using the polyurethane hot melt adhesive described in any one of claims 1 to 5.