WO2013189294A1 - 一种半互穿网络结构型聚酯/聚乙烯醇缩乙二醛热熔胶的制备方法 - Google Patents

一种半互穿网络结构型聚酯/聚乙烯醇缩乙二醛热熔胶的制备方法 Download PDF

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WO2013189294A1
WO2013189294A1 PCT/CN2013/077547 CN2013077547W WO2013189294A1 WO 2013189294 A1 WO2013189294 A1 WO 2013189294A1 CN 2013077547 W CN2013077547 W CN 2013077547W WO 2013189294 A1 WO2013189294 A1 WO 2013189294A1
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Prior art keywords
glyoxal
semi
hot melt
temperature
melt adhesive
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PCT/CN2013/077547
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English (en)
French (fr)
Inventor
李哲龙
朱万育
吴芳群
曾作祥
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KUNSHAN TIANYANG HOT MELT ADHESIVE CO LTD
SHANGHAI TIANYANG HOT MELT ADHESIVE CO LTD
East China University of Science and Technology
Original Assignee
KUNSHAN TIANYANG HOT MELT ADHESIVE CO LTD
SHANGHAI TIANYANG HOT MELT ADHESIVE CO LTD
East China University of Science and Technology
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Priority to SG2014012892A priority Critical patent/SG2014012892A/en
Priority to AU2013280006A priority patent/AU2013280006B2/en
Priority to NZ623058A priority patent/NZ623058A/en
Priority to US14/355,525 priority patent/US9346985B2/en
Priority to KR1020147014702A priority patent/KR101466677B1/ko
Publication of WO2013189294A1 publication Critical patent/WO2013189294A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to a semi-interpenetrating network structure type polyester/polyvinylglycol hot melt adhesive prepared by adding polyvinyl alcohol PVA/glyoxal.
  • polyester hot melt adhesives are obtained by transesterification or esterification reaction of a dibasic acid (ester) with a glycol, followed by decompression polymerization.
  • a method for preparing a low melting point copolyester hot melt adhesive is disclosed in U.S. Patent No. 6,255,443, and a high melting point copolyester hot melt adhesive synthesis technique is proposed in Chinese Patent No. 1340585.
  • Chinese Patent 200710043238.2 The copolyester is modified by a metal salt of sorbic acid and a copolymer of ethylene/acrylic acid to obtain a polyester hot melt adhesive with better performance.
  • the low melting point copolyester hot melt adhesive produced by the process has been added with a non-linear molecular structure raw material, such as isophthalic acid, in the preparation process, thereby breaking the linear structure of the copolyester molecule. , reduce the crystallinity and melting point of the copolyester to meet the requirements of various industries such as clothing.
  • the curing speed is also slow, which will lead to the sticking phenomenon during the processing of the lining. Therefore, the obtained hot melt adhesive is not suitable for application on the production line that needs to complete the bonding quickly. Can not be used to prepare the corresponding film or double-sided adhesive film products.
  • Melt in terms of product performance, has superior advantages over other polymerization methods. Its characteristics are: It maintains its potential reactivity during normal production, and it can be network interpenetrated at lower temperatures, reducing or eliminating thermoplasticity, ensuring improved washfastness and improved solvent resistance. Especially when compared with the non-crosslinked hot melt adhesive according to the prior art, the utility model has the advantages of low melting point and fast crystallization, which can meet the requirements of the production line of the garment industry, and can form a reticulated film or a film according to different requirements. , It is also suitable for long-term use in high temperature fields. It is a high-performance hot melt adhesive with broad application prospects.
  • the object of the present invention is to provide a method for preparing a semi-interpenetrating network structure type polyester/polyvinylglycol hot melt adhesive, which overcomes the low melting point and fast crystallization which are not available in the prior art. Defects, meeting the needs of the relevant fields.
  • the method for preparing a semi-interpenetrating network structure type polyester/polyvinylglycol hot melt adhesive comprises the following steps:
  • step 2) adding a polyvinyl alcohol/glyoxal mixture to the copolyester powder in step 2), stirring and homogenizing at room temperature to obtain a semi-interpenetrating network structure polyester/polyethylene condensed ethylene having potential reactivity Aldehyde hot melt adhesive;
  • the other dibasic ester is selected from the group consisting of dioctyl phthalate, dibutyl 1,6-adipate, dibutyl 1,10-sebacate, di-decyl 1,6-adipate Or dinonyl phthalate.
  • the molar ratio of the dinonyl phthalate to the other dibasic ester is 1: 0.2 to 0.35.
  • the other glycol is selected from the group consisting of ethylene glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, and 1,3-propanediol. More than one.
  • the molar ratio of the 1,4-butanediol to other glycols is 1: 0.1 to 0.35;
  • the molar ratio of the total ester group to the total hydroxyl group is 1: 1.1 to 1.8.
  • the total ester group refers to an ester group functional group in the diphenyl phthalate and other dibasic esters.
  • the total hydroxyl group refers to a hydroxyl functional group in the 1,4-butanediol and other glycols.
  • the polyvinyl alcohol/glyoxal mixture contains 13% to 37.5% by mass of glyoxal; the mass of the polyvinyl alcohol/glyoxal mixture is 0.2 of the mass of the copolymer powder in the step (2) % ⁇
  • the organotin catalyst is butyl stannic acid, and the amount of butyl stannic acid is 0.02% to 0.04% of the mass of dinonyl phthalate; the polycondensation catalyst is tetrabutyl titanate, tetrabutyl titanate. It is 0.02% ⁇ 0.04% of the mass of dinonyl phthalate.
  • the phosphite stabilizer is triphenyl phosphite, and the amount of triphenyl phosphite is 0.01% to 0.09% by mass of dinonyl phthalate.
  • the innovation of the present invention is that by adding a polyvinyl alcohol PVA/glyoxal mixture to the synthesized copolyester, the obtained hot melt adhesive product is characterized by: polyvinyl alcohol PVA and ethylene after baking at an appropriate temperature.
  • the reaction forms a condensation compound to form a network, and the network forms a certain degree of interpenetration with the copolyester, and a polyester/polyvinylglycol hot melt adhesive having a semi-interpenetrating network structure can be obtained.
  • the obtained semi-interpenetrating network structure type polyester/polyvinylglycol hot melt adhesive has the advantages of low melting point, fast crystallization, good heat resistance stability, resistance to dry cleaning, washing resistance and alkali resistance.
  • the preparation process is simple, and is suitable for preparing a reticulated membrane or a plastic film, and is also suitable for use in a long time high temperature environment.
  • Example 1 The invention is further illustrated by the following examples, but the invention is not limited to the examples.
  • Example 1 The invention is further illustrated by the following examples, but the invention is not limited to the examples.
  • the vacuum state is released under the protection of nitrogen to obtain copolymer particles, which are then frozen and pulverized to obtain a copolyester powder; a polyvinyl alcohol/glyoxal mixture, a polyvinyl alcohol/glyoxal mixture is added to the copolyester powder. It contains 13.0% by mass of glyoxal, and the mass of the polyvinyl alcohol/glyoxal mixture is 0.2% of the copolyester powder, and the mixture is stirred at room temperature to obtain a hot melt adhesive product. The average molecular weight of the product was 15260 g/mol and the melting point was 90-110 ° C by gel permeation chromatography and DSC respectively.
  • the melt flow rate was 120 g/10 min 60 ° C according to GB/T3682-2000.
  • the open time is 15 seconds;
  • the initial peel strength measured by FZ/T 01085-2009 is 26.08N;
  • the peel strength after washing is measured by FZ/T 01084-2000 is 22.1N;
  • /T 01083-2009 The peel strength after dry cleaning was 19.82N.
  • Example 2 The procedures and process conditions of Examples 2 to 6 were substantially the same as those of Example 1, and the changed process conditions and raw material contents are shown in Table 1, and the properties of the obtained products are also shown in Table 1.
  • Table 1 Examples 2-6 and Comparative Examples Related Process Parameters and Product Properties Example No. 2 3 4 5 6 Comparative Example Didecyl phthalate, mol 2 2 2 2 2 2 Dioctyl Phthalate , mol 0.4
  • PVA/glyoxal (37.5%)* copolyester 0.5% 1 Average molecular weight 16200 21080 23090 25580 24890 22980 Melting point, °c 98 104 102 105 104 102
  • the number in parentheses is the mass percentage of glyoxal in the PVA/glyoxal mixture.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

一种半互穿网络结构型聚酯/聚乙烯醇缩乙二酸热熔胶及其制备工艺，主要包括如下步骤：1）将一定量的对苯二甲酸二甲酯和其他二元酯、1,4-丁二醇和其他二元醇、有机锡催化剂加入反应器，氮气保护下进行酯交换反应，反应至副产物一元醇的馏出量为理论量的95%以上，酯交换反应完成；2）保温一段时间后，加入稳定剂、缩聚催化剂，继续升高反应温度，减压缩聚即得共聚物粒子，再经冷冻，粉碎，可得共聚酯粉末；3）在步骤2）的产物中加入聚乙烯醇PVA/乙二酸混合物，常温下搅泮使其混合均匀，制得目标产物。该产品在使用温度下可形成半互穿网络结构。

Description

一种半互穿网络结构型聚酯 /聚乙烯醇缩乙二醛热熔胶的制备方法
技术领域
本发明涉及一种通过添加聚乙烯醇 PVA/乙二醛制备一种半互穿网络结构 型聚酯 /聚乙烯醇缩乙二醛热熔胶。
背景技术
目前已知的聚酯热熔胶均釆用二元酸（酯） 与二元醇经酯交换或酯化反 应后， 再经减压缩聚反应得到。 如美国专利 US 6255443中揭示了一种低熔点 共聚酯热熔胶的制备方法， 中国专利 CN 1340585提出一种高熔点共聚酯热熔 胶合成技术。 中国专利 200710043238.2通过山梨酸的金属盐和一种乙婦 /丙烯 酸共聚物对共聚酯进行改性， 得到一种性能较好的聚酯热熔胶。
但从现有技术看， 所生产的低熔点共聚酯热熔胶， 在制备过程中都加入 了非线性分子结构的原料， 如间苯二曱酸， 并由此打破共聚酯分子线性结构， 降低共聚酯的结晶度和熔点， 以适应服装等各行业所需要的要求。 另一方面， 由于结晶速率慢， 其固化速度也慢， 而这将导致衬布加工过程中的粘背现象， 因此， 所得热熔胶不适用于在需要快速完成粘结的生产流水线上应用， 也不 能用于制备相应的胶膜或双面胶网膜产品。
熔胶， 在产品性能上具有其他聚合方法无法比拟的优越性。 其特点是： 它在 通常生产过程中保持其潜在的反应性， 并且它在较低温下使用时就可以进行 网络互穿， 减少或消除热塑性， 确保改进的耐洗性和改进的耐溶剂性， 尤其 是当与根据现有的技术中的非交联热熔胶相比具有熔点低， 快结晶的优点， 既可满足服装工业流水线生产要求， 又可根据不同需求， 制备成网膜或胶膜， 也适合长时间高温场下的运用， 是一种具有广泛应用前景的高性能的热熔胶。
发明内容
本发明的目的是提供一种半互穿网络结构型的聚酯 /聚乙烯醇缩乙二醛热 熔胶的制备方法， 其克服了现有技术上存在的低熔点和快结晶不能两全的缺 陷， 满足有关领域的需要。
本发明所述一种半互穿网络结构型的聚酯 /聚乙烯醇缩乙二醛热熔胶的制 备方法包括如下步骤：
1 )将对苯二曱酸二曱酯、 其他二元酯、 1,4-丁二醇、 其他二元醇和有机锡 催化剂加入反应器， 氮气保护下进行酯交换反应， 反应温度为 140〜 180。C, 气相温度保持在 65 〜 90。C, 反应至副产物一元醇的馏出量为理论量的 95% 以上， 酯交换反应完成；
2 )保温一段时间后， 加入亚磷酸酯类稳定剂和缩聚催化剂， 继续升温至 160〜 240。€进行减压缩聚反应0.5〜 1.51 , 得共聚物粒子， 再经冷冻， 粉碎， 可得共聚酯粉末；
3 )在步骤 2 ) 所述共聚酯粉末中加入聚乙烯醇 /乙二醛混合物， 常温下搅 拌使其混合均匀， 得具有潜在反应性的半互穿网络结构聚酯 /聚乙烯缩乙二醛 热熔胶；
所述的其他二元酯选自邻苯二曱酸二辛酯、 1,6-己二酸二丁酯、 1,10-癸二 酸二丁酯、 1,6-己二酸二曱酯或邻苯二曱酸二曱酯。
所述的对苯二曱酸二曱酯与其他二元酯的摩尔比为 1 : 0.2〜 0.35。
所述的其他二元醇选自乙二醇、 1,6-己二醇、 2,2,4-三曱基 -1,3-戊二醇、新 戊二醇和 1,3-丙二醇中的一种以上。
所述的 1,4-丁二醇与其他二元醇的摩尔比为 1： 0.1 〜 0.35; 总酯基和总羟基的摩尔比为 1： 1.1〜1.8。
所述总酯基是指所述对苯二曱 g史二曱酯与其他二元酯中的酯基官能团。 所述总羟基是指所述 1,4-丁二醇与其他二元醇中的羟基官能团。
所述聚乙烯醇 /乙二醛混合物中含 13%〜 37.5%质量百分比的乙二醛； 所 述聚乙烯醇 /乙二醛混合物的质量为步骤（2 )中所述共聚物粉末质量的 0.2%〜
0.5% 。
所述的有机锡催化剂为丁基锡酸， 丁基锡酸的用量为对苯二曱酸二曱酯 质量的 0.02%〜 0.04%; 所述的缩聚催化剂为钛酸四丁酯， 钛酸四丁酯的用量 为对苯二曱酸二曱酯质量的 0.02%〜 0.04%。
所述亚磷酸酯类稳定剂为亚磷酸三苯酯， 亚磷酸三苯酯的用量为对苯二 曱酸二曱酯质量的 0.01%〜 0.09%。
本发明的创新之处在于通过在所合成的共聚酯中添加聚乙烯醇 PVA/乙二 醛混合物， 所得热熔胶产品的特点是： 在适当温度焙烘后， 聚乙烯醇 PVA和 乙二 反应生成缩 化合物， 形成网络， 该网络与共聚酯形成一定程度的互 穿， 可获得具有半互穿网络结构的聚酯 /聚乙烯醇缩乙二醛热熔胶。 所制得的 半互穿网络结构型的的聚酯 /聚乙烯醇缩乙二醛热熔胶具有熔点低、 结晶快、 耐热稳定性好、 耐干洗、 耐水洗、 耐碱性的优点， 且制备工艺简单， 适合制 备网膜或胶膜， 也适合长时间高温环境下的运用。
具体实施方式
下面通过具体实施例对本发明作进一步的阐述， 但本发明并不局限于这 些实施例。 实施例 1
在带有温度计、 机械搅拌器、 回流冷凝管的四口烧瓶中， 加入对苯二曱 酸二曱酯 291g, 1,6-己二酸二曱酯 87.1g, 1,4-丁二醇 225g, 1,6-己二醇 33. lg, 2,2,4-三曱基 -1,3-戊二醇 29.2g, 丁基锡酸 0.058g、 通氮气， 加热， 并搅拌，打 开冷凝水， 当反应釜内温度达到 160。C左右时， 开始有曱醇蒸馏出， 恒定反 应温度， 待蒸出的曱醇达到理论量的 95%以上时， 酯化反应完成。 保温 0.5h, 继续升温至 220。C, 并在上述反应体系中加入亚磷酸三苯酯 0.029g,加入钛酸 四丁酯 0.058g,逐渐减压，直至体系压力 lOOPa,反应时间 30min,温度由 220。C 逐渐升高至 235°C, 缩聚反应完成。 在氮气保护下解除真空状态， 得共聚物粒 子， 再经冷冻， 粉碎， 可得共聚酯粉末； 在共聚酯粉末中加入聚乙烯醇 /乙二 醛混合物， 聚乙烯醇 /乙二醛混合物中含 13.0%质量百分比的乙二醛， 聚乙烯 醇 /乙二醛混合物的质量为共聚酯粉末的 0.2%, 常温下搅拌使其均匀， 得热熔 胶产品。 分别用凝胶渗透色傳和 DSC测定该产品平均分子量为 15260g/mol , 熔点为： 90-110°C , 按国标 GB/T3682-2000测得其熔体流动速率为： 120g/10minl60°C。 按 HG/T 3716-2003测得开放时间是 15秒； 按 FZ/T 01085-2009测得初始剥离强度是 26.08N; 按 FZ/T 01084-2000测得水洗后剥 离强度是 22.1N; 按 FZ/T 01083-2009测得干洗后剥离强度是 19.82N; 参照 水洗标准， 其中酸洗 PH=2, 碱洗 PH=11 , 酸、 碱洗后剥离强度分别为 15.25N 和 16.69N。 实施例 2〜6
实施例 2〜6与实施例 1的步骤和工艺条件基本相同， 有所变更的工艺条 件和原料配比如表 1所示， 所得产物的性能也列于表 1。 表 1 实施例 2-6和对比例相关工艺参数和产物性能 实施例号 2 3 4 5 6 对比例 对苯二曱酸二曱酯， mol 2 2 2 2 2 2 邻苯二曱酸二辛酯， mol 0.4
1,6-己二酸二丁酯， mol 0.45
1,10-癸二酸二丁酯， mol 0.6 0.6
1,6-己二酸二曱酯， mol 0.7
邻苯二曱酸二曱酯， mol 0.5
1,4-丁二醇, mol 2.1 3.2 2.7 2.9 3.6 2.7 乙二醇, mol 0.30 0.24 0.45 0.24
1,6-己二醇, mol 0.5 0.5
2,2,4-三曱基 -1,3-戊二醇， mol 0.6
新成二醇, mol 0.3 0.45 0.3
1,3-丙二醇, mol 0.24 0.4
丁基锡酸， g 0.078 0.098 0.078 0.0155 0.078 0.078 亚磷酸三苯酯， g 0.12 0.122 0.349 0.14 0.039 0.349 钛酸四丁酯， g 0.078 0.078 0.101 0.101 0.155 0.101 酯 4匕反应保温时间， min 30 40 45 50 60 45 缩聚时间， min 40 50 65 60 70 65 缩聚温度， °C 220 220 220 220 220 220
-240 -240 -240 -240 -240 -240
PVA/乙二醛 (23%)*： 共聚酯 0.3% 0.4% 1
PVA/乙二 (31%)*：共聚酯 0.2% 0.25% 1
PVA/乙二醛 (37.5%)*:共聚酯 0.5% 1 平均分子量 16200 21080 23090 25580 24890 22980 熔点， °c 98 104 102 105 104 102
〜112 〜116 〜109 〜115 〜122 〜109 融指数， g/10min(160°C) 95.7 88.3 84.7 83.2 81.9 84.7 开放时间， s 15 10 15 10 15 20 初始剥强 （N/5cm ) 21.2 21.68 23.84 23.07 24.35 23.84 水洗后剥强 （N/5cm ) 19.08 19.13 21.45 20.76 20.94 14.83 干洗后剥强 （N/5cm ) 17.84 18.02 20.26 17.99 19.84 15.92 酸洗后剥强 （N/5cm ) 13.78 12.96 15.40 14.90 15.87 11.90 碱洗后剥强 （N/5cm ) 13.64 13.72 15.68 14.20 15.20 10.26
* 括号中的数字为 PVA/乙二醛混合物中乙二醛的质量百分比

Claims

权利要求
1. 一种半互穿网络结构型聚酯 /聚乙烯缩乙二醛热熔胶的制备方法，其特征在 于， 包括如下步骤：
1 )将对苯二曱酸二曱酯、 其他二元酯、 1,4-丁二醇、 其他二元醇和有机 锡催化剂加入反应器， 氮气保护下进行酯交换反应，反应温度为 140〜 180。C, 气相温度保持在 65 〜 90。C, 反应至副产物一元醇的馏出量为理论量的 95% 以上， 酯交换反应完成；
2 )保温一段时间后， 加入亚磷酸酯类稳定剂和缩聚催化剂， 继续升温至 160〜 240。€进行减压缩聚反应0.5〜 1.51 , 得共聚物粒子， 再经冷冻， 粉碎， 可得共聚物粉末；
3 )在步骤 2 )所述共聚酯粉末中加入聚乙烯醇 /乙二醛混合物， 常温下搅 拌使其混合均匀 , 得半互穿网络结构型聚酯 /聚乙烯缩乙二醛热熔胶；
所述的其他二元酯选自邻苯二曱酸二辛酯、 1,6-己二酸二丁酯、 1,10-癸二 酸二丁酯、 1,6-己二酸二曱酯或邻苯二曱酸二曱酯；
所述的对苯二曱酸二曱酯与其他二元酯的摩尔比为 1 : 0.2〜 0.35； 所述的其他二元醇选自乙二醇、 1,6-己二醇、 2,2,4-三曱基 -1,3-戊二醇、新 戊二醇和 1,3-丙二醇中的一种以上；
所述的 1,4-丁二醇与其他二元醇的摩尔比为 1： 0.1 〜 0.35;
总酯基和总羟基的摩尔比为 1： 1.1〜1.8；
所述总酯基是指所述对苯二曱 g史二曱酯与其他二元酯中的酯基官能团； 所述总羟基是指所述 1,4-丁二醇与其他二元醇中的羟基官能团； 所述聚乙烯醇 /乙二醛混合物中含 13%〜 37.5%质量百分比的乙二醛； 所述聚乙烯醇 /乙二醛混合物的质量为步骤（ 2 )中所述共聚物粉末质量的
0.2%〜 0.5 %。
2. 根据权利要求 1所述的方法，其特征在于，所述有机锡催化剂为丁基锡酸， 丁基锡酸的用量为对苯二曱酸二曱酯质量的 0.02%〜 0.04%； 所述的缩聚催化 剂为钛酸四丁酯， 钛酸四丁酯的用量为对苯二曱酸二曱酯质量的 0.02% 〜 0.04%。
3. 根据权利要求 1所述的方法， 其特征在于， 所述亚磷酸酯类稳定剂为亚磷 酸三苯酯， 亚磷酸三苯酯的用量为对苯二曱酸二曱酯质量的 0.01%〜 0.09%。
PCT/CN2013/077547 2012-12-28 2013-06-20 一种半互穿网络结构型聚酯/聚乙烯醇缩乙二醛热熔胶的制备方法 Ceased WO2013189294A1 (zh)

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