• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A copolyester hot melt adhesive and a method of making the same are disclosed. The manufacturing process mainly involves the following steps: selecting raw materials according to predetermined ratios, the raw materials including: bisphenol A, maleic acid, terephthalic acid, another dibasic acid, 1,4-butanediol, another dibasic alcohol, catalysts and a stabilizer; Generating a prepolymer under negative pressure in a low temperature section, completing an esterification process under normal pressure in the low temperature section and completing a polycondensation step under negative pressure in a high temperature section, whereby the novel copolyester hot-melt adhesive product is finally produced. According to the disclosed copolyester hot melt adhesive product, based on maintaining the overall performance of existing conventional copolyester hot melt adhesive products, the dry cleaning resistance is significantly enhanced and is not less than a wash resistance of a polyamide hot melt adhesive, but the total cost is lower than that of the conventional polyamide hot melt adhesive.
    公开号:CH713415B1
    申请号:CH00732/18
    申请日:2016-11-30
    公开日:2020-05-29
    发明作者:Lei Heji；Li Zhelong
    申请人:Shanghai tianyang hot melt adhesive co ltd；Kunshan tianyang hot melt adhesive co ltd；
    IPC主号:
    专利说明:

    Technical field
    The present invention relates to a novel hot melt adhesive and a process for its production, and in particular a novel copolyester hot melt adhesive and a process for its production, and relates to the technical field of adhesives.
    background
    A copolyester hot melt adhesive has properties of a favorable fluidity of the melt, a high curing speed, a high adhesive force and the like and is one of the most frequently used hot melt adhesives.
    When a copolyester hot melt adhesive product is manufactured today, it is primarily obtained by performing a transesterification reaction and an esterification reaction on a dibasic acid ester, a dibasic acid and a dibasic alcohol, and then performing a polycondensation reaction under reduced pressure. For example, US6255443B discloses a method of making a low melting point copolyester hot melt adhesive, and CN1340585A discloses a method of making a high melting point polyester hot melt adhesive. CN101126006A provides a high performance copolyester hot melt adhesive made by modifying copolyester using a metal salt of sorbic acid and an ethylene / acrylic acid copolymer.
    From the perspective of the prior art, materials with non-linear molecular structure, such as isophthalic acid, are added in the manufacturing process of the copolyester hot melt adhesive, thereby breaking up the linear structure of the copolyester molecule and reducing the crystallinity and melting point of the copolyester, so that the needs of different ones Branches of industry, such as the clothing industry, can be fulfilled. Due to different methods of washing clothes, however, more and more tests show that the dry cleaning resistance of today's copolyester hot-melt adhesive products still needs to be improved.
    Summary of the invention
    The present invention seeks to solve the above technical problems by providing a novel copolyester hot melt adhesive and a process for its manufacture. The copolyester hot melt adhesive product made in the present invention has overall better performance indexes, especially a better dry cleaning resistance index than the copolyester hot melt adhesive product common today.
    The technical arrangement taken for the present invention is as follows: A novel copolyester hot melt adhesive is provided, the raw materials of which include: bisphenol A, maleic acid, terephthalic acid, another dibasic acid, 1,4-butanediol and another dibasic alcohol, the molar ratios of the raw materials being as follows:<tb> <SEP> a molar ratio of bisphenol A to maleic acid is 1.05: 1 to 1.15: 1;<tb> <SEP> a molar ratio of terephthalic acid to another dibasic acid is 1: 0.2 to 1: 0.5;<tb> <SEP> a molar ratio of 1,4-butanediol to another dibasic alcohol is 1: 0.2 to 1: 0.35;<tb> <SEP> a molar ratio of total carboxyl of terephthalic acid and another dibasic acid to total hydroxyl of 1,4-butanediol and another dibasic alcohol is 1: 1.5; and<tb> <SEP> a molar ratio of a total mole number of bisphenol A and maleic acid to a total mole number of terephthalic acid and another dibasic acid is 0.4: 1 to 0.6: 1.
    The raw materials of the novel copolyester hot melt adhesive further include catalysts and a stabilizer, the catalysts including a monobutyltinic acid catalyst and a tetrabutyltitanate catalyst, each of which, based on the mass of terephthalic acid, 0.03% to 0.06 % makes up; and the stabilizer is triphenyl phosphite, which is 0.03% to 0.07% by weight of the terephthalic acid.
    The above other dibasic acid is one selected from the group consisting of 1,10-decanedioic acid and 1,6-hexanedioic acid; and the other dibasic alcohol is one selected from the group consisting of ethanediol and 1,3-propanediol.
    [0009] The above-mentioned process for producing a novel copolyester hot melt adhesive has the following steps:<tb> 1) <SEP> Select raw materials according to the above ratios;<tb> 2) <SEP> Add bisphenol A, maleic acid and a first of the catalysts into a reaction kettle with a stirrer, heating to 160 ° C to 170 ° C and reaction at a pressure of -0.09 MPa to - 0.1 MPa for 3.0 hours to obtain a prepolymer;<tb> 3) <SEP> adding the prepolymer obtained in step (2), the terephthalic acid, the other dibasic acid, the 1,4-butanediol, the other dibasic alcohol and a second of the catalysts into a reaction kettle with a stirrer, Heating to 190 ° C to 200 ° C in a nitrogen blanket and when water is distilled from the reaction vessel, performing a thermostatic reaction until the distilled water reaches 95% or more of a theoretical amount of distillation, thereby completing an esterification reaction; and<tb> 4) <SEP> after 15 to 20 minutes holding time, add the stabilizer, further warm to 235 ° C to 240 ° C to carry out a polycondensation reaction, and after a negative pressure level has reached 80 Pa, continue the polycondensation for 60 to 70 Minutes, whereby the novel copolyester hot melt adhesive is obtained.
    In step 2) above, the added first of the catalysts is monobutyltinic acid; and in step 3) above, the added second of the catalysts is tetrabutyl titanate.
    From the novel copolyester hot melt adhesive, many things can be produced, such as adhesive particles, adhesive powder, adhesive films and the like, depending on what is currently needed.
    The innovation of the present invention is that: in the raw materials taken, both the acids and the alcohols are raw materials with a symmetrical, straight-chain, linear structure; and that using the raw materials having the linear molecular structure such as maleic acid and the like, according to certain raw material ratios, the prepolymer is first produced under negative pressure in a low temperature section, the esterification process under normal pressure is completed in the low temperature section and then the polycondensation step under negative pressure is completed in a high temperature section which ultimately produces the novel copolyester hot melt adhesive product. According to the copolyester hot melt adhesive product produced in the present invention, based on maintaining the overall performance of existing conventional copolyester hot melt adhesive products, the dry cleaning resistance is significantly enhanced and is not less than a wash resistance of a polyamide hot melt adhesive, but the total cost is lower than that of the conventional polyamide Hot melt adhesive.
    Detailed description of preferred embodiments
    The present invention is described in more detail by means of embodiments, but is not limited to these.
    Embodiment 1
    A novel copolyester hot melt adhesive is provided, the raw materials of which 56.544 g bisphenol A, 26.912 g maleic acid, 166 g terephthalic acid, 29.2 g 1,6-hexanedioic acid, 120.06 g 1,4-butanediol, 35.416 g 1 Include, 3-propanediol, 0.0996 g monobutyltinic acid, 0.0996 g tetrabutyl titanate and 0.0498 g triphenyl phosphite.
    The process for producing the novel copolyester hot melt adhesive has the following steps:<tb> (1) <SEP> Add the 56.544 g bisphenol A, the 26.912 g maleic acid and the 0.0996 g monobutyltinic acid to a reaction kettle with a stirrer, slowly warm to 160 ° C to 170 ° C and react at a pressure of -0.09 MPa to -0.1 MPa for 3.0 hours to obtain a prepolymer;<tb> (2) <SEP> Add the obtained prepolymer, the 166 g terephthalic acid, the 29.2 g 1,6-hexanedioic acid, the 120.06 g 1,4-butanediol, the 35.416 g 1,3-propanediol and the 0.0996 g of tetrabutyl titanate in a reaction kettle with a stirrer, heating to 190 ° C to 200 ° C in a nitrogen blanket, and when water is distilled from the reaction system, perform a thermostatic reaction until the amount of water distilled is 95% or more is the theoretical amount, thereby completing the esterification reaction; and<tb> (3) <SEP> after a holding time of 15 to 20 minutes, add the 0.0498 g triphenyl phosphite, further increase the reaction temperature to 235 ° C to 240 ° C, carry out a polycondensation reaction, and after the vacuum level of the system has reached 80 Pa , Continue the polycondensation for 60 to 70 minutes, whereby the novel copolyester hot melt adhesive is obtained.
    The novel copolyester hot melt adhesive product obtained by the embodiment 1 is referred to as P1.
    Embodiment 2
    A novel copolyester hot melt adhesive is provided, the raw materials of which are 70.908 g bisphenol A, 34.394 g maleic acid, 166 g terephthalic acid, 51.1 g 1,6-hexanedioic acid, 151.875 g 1,4-butanediol, 25.65 g 1 Include, 3-propanediol, 0.083 g monobutyltinic acid, 0.083 g tetrabutyl titanate and 0.083 g triphenyl phosphite.
    The process for producing the novel copolyester hot melt adhesive has the following steps:<tb> (1) <SEP> Add the 70.908 g bisphenol A, the 34.394 g maleic acid and the 0.083 g monobutyltinic acid to a reaction kettle with a stirrer, slowly warm to 160 ° C to 170 ° C and react at a pressure of -0 , 09 MPa to -0.1 MPa for 3.0 hours to obtain a prepolymer;<tb> (2) <SEP> Add the prepolymer obtained, the 166 g terephthalic acid, the 51.1 g 1,6-hexanedioic acid, the 151.875 g 1,4-butanediol, the 25.65 g 1,3-propanediol and the 0.083 g tetrabutyl titanate in a reaction kettle with a stirrer, heating to 190 ° C to 200 ° C in a nitrogen blanket, and when water is distilled from the reaction system, performing a thermostatic reaction until the amount of water distilled is 95% or more of the theoretical Amount is, whereby the esterification reaction is completed; and<tb> (3) <SEP> after a holding time of 15 to 20 minutes, add the 0.083 g triphenyl phosphite, further increase the reaction temperature to 235 ° C to 240 ° C, carry out a polycondensation reaction, and continue after the vacuum level of the system has reached 80 Pa the polycondensation for 60 to 70 minutes, whereby the novel copolyester hot melt adhesive is obtained.
    The novel copolyester hot melt adhesive product obtained by the embodiment 2 is referred to as P2.
    Embodiment 3
    A novel copolyester hot melt adhesive is provided, the raw materials of which are 91.428 g bisphenol A, 40.484 g maleic acid, 166 g terephthalic acid, 73 g 1,6-hexanedioic acid, 168.75 g 1,4-butanediol, ethanediol 23.25 g , 0.0664 g of monobutyltinic acid, 0.0664 g of tetrabutyl titanate and 0.0996 g of triphenyl phosphite.
    The process for producing the novel copolyester hot melt adhesive has the following steps:<tb> (1) <SEP> Add the 91.428 g bisphenol A, the 40.484 g maleic acid and the 0.0664 g monobutyltinic acid into a reaction kettle with a stirrer, slowly warm to 160 ° C to 170 ° C and react at a pressure of -0.09 MPa to -0.1 MPa for 3.0 hours to obtain a prepolymer;<tb> (2) <SEP> Add the obtained prepolymer, the 166 g terephthalic acid, the 73 g 1,6-hexanedioic acid, the 168.75 g 1,4-butanediol, the ethanediol 23.25 g and the 0.0664 g tetrabutyl titanate in a reaction kettle with a stirrer, heating to 190 ° C to 200 ° C in a nitrogen blanket, and when water is distilled from the reaction system, perform a thermostatic reaction until the amount of water distilled is 95% or more of the theoretical amount , thereby completing the esterification reaction; and<tb> (3) <SEP> after a holding time of 15 to 20 minutes, add the 0.0996 g triphenylphosphite, further increase the reaction temperature to 235 ° C to 240 ° C, carry out a polycondensation reaction, and after the vacuum level of the system has reached 80 Pa , Continue the polycondensation for 60 to 70 minutes, whereby the novel copolyester hot melt adhesive is obtained.
    The novel copolyester hot melt adhesive product obtained by the embodiment 3 is referred to as P3.
    Embodiment 4
    A novel copolyester hot melt adhesive is provided, the raw materials of which are 101.232 g of bisphenol A, 45.936 g of maleic acid, 166 g of terephthalic acid, 58.4 g of 1,6-hexanedioic acid, 140.4 g of 1,4-butanediol, ethanediol 33, Include 48 g, 0.0498 g monobutyltinic acid, 0.0498 g tetrabutyl titanate and 0.1162 g triphenyl phosphite.
    The process for producing the novel copolyester hot melt adhesive has the following steps:<tb> (1) <SEP> Add the 101.232 g bisphenol A, the 45.936 g maleic acid and the 0.0498 g monobutyltinic acid into a reaction kettle with a stirrer, slowly warm to 160 ° C to 170 ° C and react at a pressure of -0.09 MPa to -0.1 MPa for 3.0 hours to obtain a prepolymer;<tb> (2) <SEP> Add the obtained prepolymer, the 166 g terephthalic acid, the 58.4 g 1,6-hexanedioic acid, the 140.4 g 1,4-butanediol, the ethanediol 33.48 g and the 0 , 0498 g of tetrabutyl titanate in a reaction kettle with a stirrer, heating to 190 ° C to 200 ° C in a nitrogen blanket, and when water is distilled from the reaction system, perform a thermostatic reaction until the amount of water distilled is 95% or more of the theoretical Amount is, whereby the esterification reaction is completed; and<tb> (3) <SEP> after a holding time of 15 to 20 minutes, add the 0.1162 g triphenyl phosphite, further increase the reaction temperature to 235 ° C to 240 ° C, carry out a polycondensation reaction, and after the vacuum level of the system has reached 80 Pa , Continue the polycondensation for 60 to 70 minutes, whereby the novel copolyester hot melt adhesive is obtained.
    The novel copolyester hot melt adhesive product obtained by the embodiment 4 is referred to as P4.
    Embodiment 5
    A novel copolyester hot melt adhesive is provided, the raw materials of which 56.544 g bisphenol A, 26.912 g maleic acid, 166 g terephthalic acid, 1.10-decanedioic acid 40.4 g, 120.06 g 1,4-butanediol, 35.416 g 1 Include, 3-propanediol, 0.0996 g monobutyltinic acid, 0.0996 g tetrabutyl titanate and 0.0498 g triphenyl phosphite.
    The process for producing the novel copolyester hot melt adhesive has the following steps:<tb> (1) <SEP> Add the 56.544 g bisphenol A, the 26.912 g maleic acid and the 0.0996 g monobutyltinic acid to a reaction kettle with a stirrer, slowly warm to 160 ° C to 170 ° C and react at a pressure of -0.09 MPa to -0.1 MPa for 3.0 hours to obtain a prepolymer;<tb> (2) <SEP> Add the prepolymer obtained, the 166 g terephthalic acid, the 1,10-hexanedioic acid 40.4 g, the 140.4 g 1,4-butanediol, the 35.416 g 1,3-propanediol and the 0.0996 g of tetrabutyl titanate in a reaction kettle with a stirrer, heating to 190 ° C to 200 ° C in a nitrogen blanket, and when water is distilled from the reaction system, performing a thermostatic reaction until the amount of water distilled is 95% or more is the theoretical amount, thereby completing the esterification reaction; and<tb> (3) <SEP> after a holding time of 15 to 20 minutes, add the 0.0498 g triphenyl phosphite, further increase the reaction temperature to 235 ° C to 240 ° C, carry out a polycondensation reaction, and after the vacuum level of the system has reached 80 Pa , Continue the polycondensation for 60 to 70 minutes, whereby the novel copolyester hot melt adhesive is obtained.
    The novel copolyester hot melt adhesive product obtained by the embodiment 5 is referred to as P5.
    Embodiment 6
    A novel copolyester hot melt adhesive is provided, the raw materials of which are 70.908 g of bisphenol A, 34.394 g of maleic acid, 166 g of terephthalic acid, 1.10-decanedioic acid, 70.7 g, 151.875 g of 1,4-butanediol, 25.65 g of 1 Include, 3-propanediol, 0.083 g monobutyltinic acid, 0.083 g tetrabutyl titanate and 0.083 g triphenyl phosphite.
    The process for producing the novel copolyester hot melt adhesive has the following steps:<tb> (1) <SEP> Add the 70.908 g bisphenol A, the 34.394 g maleic acid and the 0.083 g monobutyltinic acid to a reaction kettle with a stirrer, slowly warm to 160 ° C - 170 ° C and react at a pressure of -0 , 09 MPa to -0.1 MPa for 3.0 hours to obtain a prepolymer;<tb> (2) <SEP> Add the prepolymer obtained, the 166 g terephthalic acid, the 1,10-decanedioic acid 70.7 g, the 151.875 g 1,4-butanediol, the 25.65 g 1,3-propanediol and the 0.083 g tetrabutyl titanate in a reaction kettle with a stirrer, heating to 190 ° C to 200 ° C in a nitrogen blanket, and when water is distilled from the reaction system, performing a thermostatic reaction until the amount of water distilled is 95% or more of the theoretical Amount is, whereby the esterification reaction is completed; and<tb> (3) <SEP> after a holding time of 15 to 20 minutes, add the 0.083 g triphenyl phosphite, further increase the reaction temperature to 235 ° C to 240 ° C, carry out a polycondensation reaction, and continue after the vacuum level of the system has reached 80 Pa the polycondensation for 60 to 70 minutes, whereby the novel copolyester hot melt adhesive is obtained.
    The novel copolyester hot melt adhesive product obtained by the embodiment 6 is referred to as P6.
    Embodiment 7
    A novel copolyester hot melt adhesive is provided, the raw materials of which are 91.428 g bisphenol A, 40.484 g maleic acid, 166 g terephthalic acid, 1.10-decanedioic acid 101 g, 168.75 g 1,4-butanediol, ethanediol 23.25 g , 0.0664 g of monobutyltinic acid, 0.0664 g of tetrabutyl titanate and 0.0996 g of triphenyl phosphite.
    The process for producing the novel copolyester hot melt adhesive has the following steps:<tb> (1) <SEP> Add the 91.428 g bisphenol A, the 40.484 g maleic acid and the 0.0664 g monobutyltinic acid into a reaction kettle with a stirrer, slowly warm to 160 ° C to 170 ° C and react at a pressure of -0.09 MPa to -0.1 MPa for 3.0 hours to obtain a prepolymer;<tb> (2) <SEP> Add the obtained prepolymer, the 166 g terephthalic acid, the 1,10-decanedioic acid 101 g, the 168.75 g 1,4-butanediol, the ethanediol 23.25 g and the 0.0664 g tetrabutyl titanate in a reaction kettle with a stirrer, heating to 190 ° C to 200 ° C in a nitrogen blanket, and when water is distilled from the reaction system, perform a thermostatic reaction until the amount of water distilled is 95% or more of the theoretical amount , thereby completing the esterification reaction; and<tb> (3) <SEP> after a holding time of 15 to 20 minutes, add the 0.0996 g triphenyl phosphite, further increase the reaction temperature to 235 ° C to 240 ° C, carry out a polycondensation reaction, and after the vacuum level of the system has reached 80 Pa , Continue the polycondensation for 60 to 70 minutes, whereby the novel copolyester hot melt adhesive is obtained.
    The novel copolyester hot melt adhesive product obtained by the embodiment 7 is referred to as P7.
    Embodiment 8
    A novel copolyester hot melt adhesive is provided, the raw materials of which are 101.232 g bisphenol A, 45.936 g maleic acid, 166 g terephthalic acid, 1.10-decanedioic acid 80 g, 140.4 g 1,4-butanediol, ethanediol 33.48 g , 0.0498 g monobutyltinic acid, 0.0498 g tetrabutyl titanate and 0.1162 g triphenyl phosphite.
    The process for producing the novel copolyester hot melt adhesive has the following steps:<tb> (1) <SEP> Add the 101.232 g bisphenol A, the 45.936 g maleic acid and the 0.0498 g monobutyltinic acid into a reaction kettle with a stirrer, slowly warm to 160 ° C to 170 ° C and react at a pressure of -0.09 MPa to -0.1 MPa for 3.0 hours to obtain a prepolymer;<tb> (2) <SEP> Add the obtained prepolymer, the 166 g terephthalic acid, the 1,10-decanedioic acid 80 g, the 140.4 g 1,4-butanediol, the ethanediol 33.48 g and the 0.0498 g tetrabutyl titanate in a reaction kettle with a stirrer, heating to 190 ° C to 200 ° C in a nitrogen blanket, and when water is distilled from the reaction system, perform a thermostatic reaction until the amount of water distilled is 95% or more of the theoretical amount , thereby completing the esterification reaction; and<tb> (3) <SEP> after a holding time of 15 to 20 minutes, add the 0.1162 g triphenyl phosphite, further increase the reaction temperature to 235 ° C to 240 ° C, carry out a polycondensation reaction, and after the vacuum level of the system has reached 80 Pa , Continue the polycondensation for 60 to 70 minutes, whereby the novel copolyester hot melt adhesive is obtained.
    The novel copolyester hot melt adhesive product obtained by the embodiment 8 is referred to as P8.
    Sample test
    The products P1 to P8 obtained are subjected to sample tests. Reference is made to ISO 11357 for the melting point test, reference GB 11402 for the peel strength test, reference GB / T 8629 for the washing resistance index and reference FZ / T 01083 for the dry cleaning resistance index. The individual test results are shown in Table 1 below.
    Table 1: Performance testing of the samples.
    [0039]<tb> P1 <SEP> 125 <SEP> 45.23 <SEP> 10.5 <SEP> 16.2 <SEP> 15.4<tb> P2 <SEP> 121 <SEP> 46.51 <SEP> 9.7 <SEP> 14.7 <SEP> 16<tb> P3 <SEP> 126 <SEP> 44.89 <SEP> 9.2 <SEP> 15.8 <SEP> 16.3<tb> P4 <SEP> 125 <SEP> 45.91 <SEP> 10.3 <SEP> 13.9 <SEP> 15.7<tb> P5 <SEP> 124 <SEP> 44.6 <SEP> 11 <SEP> 14.5 <SEP> 14<tb> P6 <SEP> 122 <SEP> 45.03 <SEP> 9 <SEP> 15.5 <SEP> 14.7<tb> P7 <SEP> 123 <SEP> 46.02 <SEP> 8.9 <SEP> 16 <SEP> 15.3<tb> P8 <SEP> 124 <SEP> 46.35 <SEP> 10.9 <SEP> 15.2 <SEP> 15.9
    Today, similar, conventional copolyester hot melt adhesives (with a melting point of, for example, 120 ° C to 130 ° C) generally have a peel strength of about 40 N / cm, a wash loss rate at 40 ° C of 15% to 20% and one Wash loss rate at 60 ° C from 25% to 35%, but after dry cleaning, the loss rate is generally over 90% and even approaching 100%.
    From Table 1 above it is clear that the copolyester hotmelt adhesive which is produced on the basis of the present invention has hardly any difference in melting point in comparison with conventional copolyester hotmelt adhesive products and is also well suited for construction and handling ; the peel strength is slightly better than that of conventional products and reaches about 45 N / cm; wash loss rates at 40 ° C and 60 ° C are also better than those of conventional products and are about 10% and 15% lower, respectively; and the dry cleaning loss rate is much better than that of conventional products and is limited to 14% to 17%.
    权利要求:
    Claims (4)
    [1]
    1. Copolyester hot melt adhesive available from raw materials comprising: bisphenol A, maleic acid, terephthalic acid, another dibasic acid selected from the group consisting of 1,10-decanedioic acid and 1,6-hexanedioic acid, 1,4-butanediol and another dibasic alcohol , selected from the group consisting of ethanediol and 1,3-propanediol, the molar ratios of the raw materials being as follows:the molar ratio of bisphenol A to maleic acid is 1.05: 1 to 1.15: 1;which is a molar ratio of terephthalic acid to the other dibasic acid is 1: 0.2 to 1: 0.5;that is a molar ratio of 1,4-butanediol to the other dibasic alcohol is 1: 0.2 to 1: 0.35;the molar ratio of total carboxyl of terephthalic acid and the other dibasic acid to total hydroxyl of 1,4-butanediol and the other dibasic alcohol is 1: 1.5; anda molar ratio of a total mol number of bisphenol A and maleic acid to a total mol number of terephthalic acid and the other dibasic acid is 0.4: 1 to 0.6: 1.
    [2]
    2. A copolyester hot melt adhesive according to claim 1, wherein the raw materials further comprise catalysts and a stabilizer, the catalysts comprising monobutyltinic acid and tetrabutyltitanate, each representing 0.03% to 0.06% by weight of the terephthalic acid; and wherein the stabilizer is triphenyl phosphite, which is 0.03% to 0.07% by weight of the terephthalic acid.
    [3]
    3. A method of making a copolyester hot melt adhesive comprising the following steps:I) Selecting raw materials according to predetermined ratios, the raw materials bisphenol A, maleic acid, terephthalic acid, another dibasic acid selected from the group consisting of 1,10-decanedioic acid and 1,6-hexanedioic acid, 1,4-butanediol, another dibasic alcohol selected from the group consisting of ethanediol and 1,3-propanediol, catalysts and a stabilizer;II) Add bisphenol A, the maleic acid and a first of the catalysts into a reaction kettle with a stirrer, heating to 160 ° C to 170 ° C and reaction at a pressure of -0.09 MPa to -0.1 MPa for 3 , 0 hours to obtain a prepolymer;III) Add the prepolymer obtained in step 2), the terephthalic acid, the other dibasic acid, the 1,4-butanediol, the other dibasic alcohol and a second of the catalysts into a reaction kettle with a stirrer, heating to 190 ° C. to 200 ° C in a protective nitrogen atmosphere, and when water is distilled from the reaction vessel, performing a thermostatic reaction until the distilled water reaches 95% or more of a theoretical amount of distillation, thereby completing an esterification reaction; andIV) after 15 to 20 minutes of holding time, add the stabilizer, further warm to 235 ° C to 240 ° C to carry out a polycondensation reaction, and after a negative pressure level has reached 80 Pa, continue the polycondensation for 60 to 70 minutes, resulting in the novel copolyester - hot melt adhesive is obtained;where the predetermined ratios of raw materials are as follows:which is a molar ratio of bisphenol A to maleic acid 1.05: 1 to 1.15: 1;the molar ratio of terephthalic acid to the other dibasic acid is 1: 0.2 to 1: 0.5;the molar ratio of 1,4-butanediol to the other dibasic alcohol is 1: 0.2 to 1: 0.35;which is a molar ratio of total carboxyl of terephthalic acid and the other dibasic acid to total hydroxyl of 1,4-butanediol and the other dibasic alcohol is 1: 1.5;a molar ratio of a total mole number of bisphenol A and maleic acid to a total mole number of terephthalic acid and another dibasic acid is 0.4: 1 to 0.6: 1;the first of the catalysts and the second of the catalysts are selected from the group consisting of monobutyltinic acid and tetrabutyltitanate and each constitute 0.03% to 0.06% based on the mass of terephthalic acid; andthe stabilizer is triphenyl phosphite which, based on the mass of terephthalic acid, makes up 0.03% to 0.07%.
    [4]
    4. A method of making a copolyester hot melt adhesive according to claim 3, wherein the first of the catalysts added in step 2) is monobutyltinic acid and the second of the catalysts added in step 3) is tetrabutyl titanate.
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    DE4328800A1|1995-03-02|Low-pill and flame-retardant modified polyester, process for their production and structures formed therefrom
    DE1719123A1|1971-08-05|Gluing and covering of plasticized polyvinyl chloride plastics
    DE2400228A1|1974-08-01|PROCESS FOR MANUFACTURING PIGMENTED POLYAETHYLENE TEREPHTHALATE
    DE611056C|1935-03-22|Process for the production of resinous condensation products from polybasic organic acids and saturated aliphatic polyoxymonocarboxylic acids
    DE1520090A1|1969-05-29|Process for the production of mixed polyesters
    AT205234B|1959-09-10|Process for the production of polyesters
    DE949683C|1956-09-27|Process for the production of artificial structures, such as threads or fibers, from melted polyesters or mixed polyesters
    DE676407C|1939-06-03|Process for the production of valuable nitrogenous products
    DE932633C|1955-09-05|Process for the production of rubber-like plastics
    同族专利:
    公开号 | 公开日
    CN105348497A|2016-02-24|
    DE112016005594T5|2018-10-31|
    CN105348497B|2018-01-02|
    US10501666B2|2019-12-10|
    US20180346772A1|2018-12-06|
    KR102177942B1|2020-11-12|
    WO2017097157A1|2017-06-15|
    KR20180098287A|2018-09-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS6312110B2|1980-09-16|1988-03-17|Dainippon Ink & Chemicals|
    JPS63218780A|1987-03-05|1988-09-12|Toray Ind Inc|Powdery adhesive and powdery adhesive for liquid crystal element utilizing said adhesive|
    DE19510314A1|1995-03-22|1996-09-26|Huels Chemische Werke Ag|Polyester for the bonding of textiles|
    DE19510315A1|1995-03-22|1996-09-26|Huels Chemische Werke Ag|Hotmelt adhesive composition for coating of deposit material|
    JPH10237412A|1997-02-24|1998-09-08|Bando Chem Ind Ltd|Hot melt adhesive|
    DE19831366A1|1998-07-13|2000-01-27|Inventa Ag|Deep-melting copolyester or copolyetherester hotmelt adhesives|
    CN1138841C|2000-08-29|2004-02-18|上海理日科技发展有限公司|Process for preparing polyester thermosol with high smelting point|
    JP5192681B2|2005-10-27|2013-05-08|三洋化成工業株式会社|Hydrophilic hot melt adhesive|
    CN101126006B|2007-06-29|2010-05-19|上海天洋热熔胶有限公司|Method for preparing polyester thermosol|
    CN101463240A|2009-01-15|2009-06-24|上海天洋热熔胶有限公司|Preparation of polyester hot-melt adhesive for net film|
    CN101735758A|2009-12-24|2010-06-16|昆山天洋热熔胶有限公司|Polyester hot melt adhesive used for back glue of carpet and preparation method thereof|
    CN102102003B|2010-12-14|2012-08-15|上海天洋热熔胶有限公司|Polyester hot melt adhesive for making films and preparation method thereof|
    CN103013415B|2012-12-28|2013-12-04|昆山天洋热熔胶有限公司|Semi-interpenetrating-network-structure polyester/polyvinyl aldehyde hot-melt adhesive and preparation technique thereof|
    CN103483572B|2013-10-16|2015-08-05|上海天洋热熔粘接材料股份有限公司|A kind of preparation method of low-melting-point washable polyester hot-melt adhesive|
    CN105348497B|2015-12-07|2018-01-02|上海天洋热熔粘接材料股份有限公司|A kind of novel copolymerized ester PUR and preparation method thereof|CN105348497B|2015-12-07|2018-01-02|上海天洋热熔粘接材料股份有限公司|A kind of novel copolymerized ester PUR and preparation method thereof|
    KR102356309B1|2017-11-20|2022-01-28|에스케이케미칼 주식회사|Polyester resin composition for hot-melt adhesive|
    CN108624272B|2018-05-28|2020-12-08|南通天洋新材料有限公司|Copolyester hot melt adhesive and preparation method thereof|
    CN111518510B|2020-04-23|2021-10-26|浙江恒澜科技有限公司|Preparation method of long-carbon-chain polyesteramide hot melt adhesive containing side hydrocarbon groups|
    KR102184968B1|2020-07-21|2020-12-02|명신기연|Method for manufacturing reactive hot-melt adhesive and adhesive manufactured by the same|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CN201510881844.6A|CN105348497B|2015-12-07|2015-12-07|A kind of novel copolymerized ester PUR and preparation method thereof|
    PCT/CN2016/107883|WO2017097157A1|2015-12-07|2016-11-30|Novel copolyester hot-melt adhesive and preparation method therefor|
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