• 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:
    There is disclosed a process for making a high viscosity polyester hotmelt adhesive having partially sensitive viscosity-temperature properties comprising the steps of: i) esterifying terephthalic acid, isophthalic acid, dodecanedioic acid, adipic acid, butanediol, dipropylene glycol and hexanediol in the presence of tetrabutyl titanate, referred to as Catalyst, and ii) adding an antioxidant to a product resulting from step i) and polycondensation at reduced pressure, followed by obtaining the low viscosity high viscosity polyester hotmelt adhesive having a melting point of 130 ° C-135 ° C and has partially sensitive viscosity-temperature properties.
    公开号:CH711540B1
    申请号:CH00068/17
    申请日:2015-07-20
    公开日:2017-06-30
    发明作者:Li Zhelong；Zhu Wanyu；Lei Heji；Wu Fangqun；Zeng Zuoxiang
    申请人:Kunshan tianyang hot melt adhesive co ltd；Shanghai tianyang hot melt adhesive co ltd；Univ East China Science & Tech；
    IPC主号:
    专利说明:

    Description Technical Field The present invention relates to the production of polyester hot melt adhesives, and more particularly to a process for the preparation of a low viscosity high viscosity polyester hot melt adhesive wherein the viscosity undergoes a significant reduction within a specific temperature range.
    Background Preparation of a high-viscosity polyester by secondary processing of a corresponding low viscosity polyester tends to require a complicated process. For example, Chinese Patent Publication No. CN 1 317 030 A describes a process in which a low viscosity polyester is produced and blended with oxazoline to form a matrix, which is then blended with a high viscosity polyester for subsequent processing. This process is expensive and the oxazoline used is biologically hazardous and dangerous to the environment. To overcome such shortcomings of the prior art, the present invention provides a process for producing a polyester hotmelt adhesive having a low melting point of 130 ° C-135 ° C, a high viscosity of 700-750 Pa · s (at 160 ° C) ° C) and has partially sensitive viscosity-temperature properties.
    Summary of the Invention The present invention provides a process for producing a high viscosity polyester hotmelt adhesive having partially sensitive viscosity-temperature properties, comprising the steps of: 1) esterifying in a dibasic acid, dihydric alcohol, and esterification reactor a catalyst in a predetermined ratio at a temperature of 140 ° C to 200 ° C and completion of the esterification when an amount of distilled water reaches 93% or more of the theoretical amount of distilled water, and 2) adding an antioxidant to an off step 1), polycondensation at reduced pressure at 240 ° C-245 ° C and 50 Pa-80 Pa for 1.0 hour to obtain the high-viscosity polyester hot-melt adhesive having partially sensitive viscosity-temperature characteristics, in which the Viscosity decreases by 75% -80% when the temperature increases from 160 ° C to 170 ° C w The dibasic acid is a mixture of terephthalic acid, isophthalic acid, butanedioic acid, dodecanedioic acid and adipic acid.
    The dihydric alcohol is a mixture of butanediol, dipropylene glycol and hexanediol.
    The dibasic acid and the dihydric alcohol are present in a molar ratio of 1: 1.50.
    The terephthalic acid and the isophthalic acid are present in a molar ratio of 1: 0.10 to 1: 0.15.
    The terephthalic acid and the butanedioic acid are present in a molar ratio of 1: 0.20 to 1: 0.30.
    The terephthalic acid and dodecanedioic acid are present in a molar ratio of 1: 0.1 to 1: 0.25.
    The terephthalic acid and adipic acid are present in a molar ratio of 1: 0.40 to 1: 0.50.
    The butanediol and the dipropylene glycol are present in a molar ratio of 1: 0.20 to 1: 0.60.
    The butanediol and the hexanediol are present in a molar ratio of 1: 0.30 to 1: 0.70.
    The antioxidant is one selected from the group consisting of trimethyl phosphate, antioxidant 168 and antioxidant 1010.
    The catalyst may be tetrabutyl titanate present in a weight ratio of 0.03% -0.06% of the dibasic acid.
    The antioxidant may be present in a weight ratio of 0.5% -0.8% of the dibasic acid.
    The present invention is inventive in that a high-viscosity polyester hot-melt adhesive having a melting point of 130 ° C-135 ° C and partially sensitive viscosity-temperature properties, from a specific composition of the starting materials using the simple esterification process can be obtained.
    Performance tests: The performance of the products prepared in the following experimental and comparative examples were tested according to the following standards: Melting points - ISO 11357; and Viscosities - GB / T 7193.1-1987.
    The polyester hot-melt adhesive according to the present invention has good fluidity and leveling properties when applied at a temperature of 170 ° C or higher. During the cooling will be his
    Viscosity experience an immediate increase at a temperature of about 160 ° C, which in accordance with an immediate increased adhesion between the objects to which it has been applied, is provided and a shift between them under the action of an external force is prevented. The polyester hot-melt adhesive according to the present invention can be directly used for or used for the production of films useful in adhesion in the fields of clothing, shoe materials, heat transfer printing, trademarks, carpets, wood and the like.
    DETAILED DESCRIPTION The present invention will now be described in further detail by way of the following embodiments, which, however, are not intended to limit the invention in any way.
    Example 1 In a 1 L reactor equipped with a stirrer, a temperature measuring system, a rectification column and a reflux condenser, 166,000 g (1,000 mol) of terephthalic acid, 19.920 g (0.120 mol) of isophthalic acid, 65.700 g (0.450 mol ) Adipic acid, 34.500 g (0.150 mol) of dodecanedioic acid, 33.040 g (0.280 mol) of butanedioic acid, 135.000 g (1.500 mol) of butanediol, 120.600 g (0.900 mol) of dipropylene glycol, 70.800 g (0.600 mol) of hexanediol and 0.115 g of tetrabutyl titanate heated gradually to 90 ° C, followed by initialization of stirring. As the temperature approached 140 ° C, distillation began at a temperature of 98 ° C-102 ° C. The temperature was further raised to about 200 ° C, and the esterification was completed when the amount of distilled water reached 93% or more of the theoretical amount.
    Thereafter, in addition, 1.717 g of antioxidant 168 were added to induce a polycondensation, and the temperature was gradually increased to 242 ° C and held at this temperature. Then, the pressure in the reactor was reduced and kept at 60 Pa for 1.0 hour, whereby the polycondensation was completed. Thereafter, nitrogen was introduced to release the vacuum, followed by a hot discharge into cold water, whereby white gel-like rods were obtained, which were then pelletized to give product 2. It was determined that the product has a DSC melting point of 132 ° C, a viscosity of 709 Pa-s at 160 ° C and a viscosity of 146 Pa-s at 170 ° C, thus satisfying the above-mentioned standard.
    Example 2 Into a 1 L reactor equipped with a stirrer, a temperature measuring system, a rectification column and a reflux condenser, 166,000 g (1,000 mol) of terephthalic acid, 16.600 g (0.100 mol) of isophthalic acid, 65.700 g (0.450 mol ) Adipic acid, 57.500 g (0.250 mol) of dodecanedioic acid, 29.500 g (0.250 mol) of butanedioic acid, 135.000 g (1.500 mol) of butanediol, 110.550 g (0.825 mol) of dipropylene glycol, 88.500 g (0.750 mol) of hexanediol and 0.123 g of tetrabutyl titanate was gradually heated to 90 ° C, followed by initialization of stirring. As the temperature approached 140 ° C, distillation began at a temperature of 98 ° C-102 ° C. The temperature was further raised to about 200 ° C, and the esterification was completed when the amount of distilled water reached 93% or more of the theoretical value.
    Then, 2.141 g of antioxidant 168 was further added to induce polycondensation, and the temperature was gradually raised to 240 ° C and maintained at that temperature. The pressure in the reactor was then reduced to 60 Pa and held for 1.0 hour, completing the polycondensation. Thereafter, nitrogen was introduced to release the vacuum, followed by a hot discharge into cold water, whereby white gel-like rods were obtained, which were then pelletized to give Product 3. It was determined that the product has a DSC melting point of 130 ° C, a viscosity of 730 Pa-s at 160 ° C and a viscosity of 151 Pa-s at 170 ° C, thus satisfying the above-mentioned standard.
    Example 3 Into a 1 L reactor equipped with a stirrer, a temperature measuring system, a rectification column and a reflux condenser, 166,000 g (1,000 mol) of terephthalic acid, 21.580 g (0.130 mol) of isophthalic acid, 58.400 g (0.400 mol Adipic acid, 39.100 g (0.170 mol) of dodecanedioic acid, 23.600 g (0.200 mol) of butanedioic acid, 135,000 g (1.500 mol) of butanediol, 40.200 g (0.300 mol) of dipropylene glycol, 123.900 g (1.050 mol) of hexanediol and 0.143 g of tetrabutyl titanate are added thereto was gradually heated to 90 ° C, followed by initialization of stirring. As the temperature approached 140 ° C, distillation began at a temperature of 98 ° C-102 ° C. The temperature was further raised to about 200 ° C, and the esterification was completed when the amount of distilled water reached 93% or more of the theoretical value.
    Thereafter, in addition, 1.853 g of antioxidant 168 was added to induce polycondensation, and the temperature was gradually raised to 244 ° C and maintained at that temperature. The pressure in the reactor was then reduced to 60 Pa and held for 1.0 hour, completing the polycondensation. Thereafter, nitrogen was introduced to release the vacuum, followed by a hot discharge into cold water, whereby white gel-like rods were obtained, which were then pelletized to give product 4. It was determined
    权利要求:
    Claims (3)
    [1]
    that the product has a DSC melting point of 133 ° C, a viscosity of 740 Pa-s at 160 ° C and a viscosity of 161 Pa-s at 170 ° C, thus satisfying the above-mentioned standard. Comparative Example 1 Into a 1 L reactor equipped with a stirrer, a temperature measuring system, a rectification column and a reflux condenser, 166,000 g (1,000 mol) of terephthalic acid, 58,100 g (0.350 mol) of isophthalic acid, 87,600 g (0.600 mol ) Adipic acid, 46,000 g (0.200 mol) of dodecanedioic acid, 29.500 g (0.250 mol) of butanedioic acid, 135,000 g (1,500 mol) of butanediol, 140,700 g (1,050 mol) of dipropylene glycol, 123,900 g (1,050 mol) of hexanediol and 0.107 g of tetrabutyl titanate was gradually heated to 90 ° C, followed by initialization of stirring. As the temperature approached 140 ° C, distillation began at a temperature of 98 ° C-102 ° C. The temperature was further raised to about 200 ° C, and the esterification was completed when the amount of distilled water reached 93% or more of the theoretical value. Thereafter, in addition, 2.861 g of antioxidant 168 was added to induce polycondensation, and the temperature was gradually raised to 240 ° C and maintained at that temperature. The pressure in the reactor was then reduced to 60 Pa and held for 1.0 hour, completing the polycondensation. Thereafter, nitrogen was introduced to release the vacuum, followed by a hot discharge into cold water, whereby white gel-like rods were obtained, which were then pelletized to give product C1. It was determined that the product has a DSC melting point of 148 ° C, a viscosity of 210 Pa-s at 160 ° C and a viscosity of 181 Pa-s at 170 ° C, thus satisfying the above-mentioned standard. The foregoing description is merely a basic illustration based on the concept of the present invention and any equivalent variations made in accordance with the subject invention are considered to be within the scope thereof. claims
    A process for producing a high-viscosity polyester hotmelt adhesive having viscosity-temperature properties, comprising the steps of: 1) esterifying in a dibasic acid esterification reactor, a dihydric alcohol and a catalyst in a predetermined ratio at a temperature of 140 ° C to 200 ° C and completion of the esterification, when an amount of distilled water reaches 93% or more of the theoretical amount of distilled water, and 2) addition of an antioxidant to a product obtained from step 1), polycondensation at reduced pressure at 240 ° C-245 ° C and 50 Pa-80 Pa for 1.0 hour to obtain the high-viscosity polyester hot-melt adhesive having viscosity-temperature properties, which has a viscosity of 700 Pa-s-750 Pa-s at 160 ° C, and its viscosity decreases by 75% -80% when the temperature is raised from 160 ° C to 170 ° C, the viscosity being according to China National Standard GB / T 7193. 1-1987, wherein: the dibasic acid is a mixture of terephthalic acid, isophthalic acid, butanedioic acid, dodecanedioic acid and adipic acid; the dihydric alcohol is a mixture of butanediol, dipropylene glycol and hexanediol; the dibasic acid and the dihydric alcohol are present in a molar ratio of 1: 1.50; the terephthalic acid and the isophthalic acid are present in a molar ratio of 1: 0.10 to 1: 0.15; the terephthalic acid and the butanedioic acid are present in a molar ratio of 1: 0.20 to 1: 0.30; the terephthalic acid and the dodecanedioic acid are present in a molar ratio of 1: 0.1 to 1: 0.25; the terephthalic acid and the adipic acid are present in a molar ratio of 1: 0.40 to 1: 0.50; the butanediol and the dipropylene glycol are present in a molar ratio of 1: 0.20 to 1: 0.60; the butanediol and the hexanediol are present in a molar ratio of 1: 0.30 to 1: 0.70; and the antioxidant is one selected from the group consisting of trimethyl phosphate, antioxidant 168, and antioxidant 1010.
    [2]
    A process according to claim 1, wherein the catalyst is tetrabutyl titanate present in a weight ratio of 0.03% -0.06% of the dibasic acid.
    [3]
    3. The method according to claim 1, wherein the antioxidant is present in a weight ratio of 0.5% -0.8% of the dibasic acid.
    类似技术:
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2019011529A1|2017-07-13|2019-01-17|Henkel Ag & Co. Kgaa|Semi-crystalline mixture of polyester polyols, and use thereof|JPS6017359B2|1978-09-20|1985-05-02|Asahi Chemical Ind|
    JP3629644B2|1994-06-22|2005-03-16|東レ・デュポン株式会社|Resin composition, method for producing the same, and hot melt adhesive comprising the same|
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    JP5472206B2|2011-05-30|2014-04-16|東洋紡株式会社|adhesive|
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    CN103184027B|2011-12-28|2015-05-13|上海轻工业研究所有限公司|Low-viscosity polyester hot melt adhesive and preparation method thereof|
    CN102732202A|2012-06-16|2012-10-17|上海天洋热熔胶有限公司|Preparation method for non-crystalline low-melting point polyester hot melt adhesive|
    CN104119829B|2014-07-22|2015-11-18|昆山天洋热熔胶有限公司|A kind of high viscosity and the preparation method of the polyester hot-melt adhesive of viscosity-temperature characteristics local sensitivity|CN104119829B|2014-07-22|2015-11-18|昆山天洋热熔胶有限公司|A kind of high viscosity and the preparation method of the polyester hot-melt adhesive of viscosity-temperature characteristics local sensitivity|
    CN106318305B|2016-08-30|2021-08-10|上海天洋热熔粘接材料股份有限公司|Preparation method of polyester hot melt adhesive for film making|
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    法律状态:
    2017-01-31| PK| Correction|Free format text: BERICHTIGUNG INHABER |
    2017-09-29| PCAR| Change of the address of the representative|Free format text: NEW ADDRESS: BELLERIVESTRASSE 203 POSTFACH, 8034 ZUERICH (CH) |
    2020-02-28| PL| Patent ceased|
    优先权:
    申请号 | 申请日 | 专利标题
    CN201410348224.1A|CN104119829B|2014-07-22|2014-07-22|A kind of high viscosity and the preparation method of the polyester hot-melt adhesive of viscosity-temperature characteristics local sensitivity|
    PCT/CN2015/084459|WO2016011923A1|2014-07-22|2015-07-20|Method for preparing polyester hot melt adhesive with high viscosity and locally sensitive viscosity-temperature property|
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