CN103013415B - 一种半互穿网络结构型聚酯/聚乙烯醛热熔胶及其制备工艺 - Google Patents

一种半互穿网络结构型聚酯/聚乙烯醛热熔胶及其制备工艺 Download PDF

Info

Publication number
CN103013415B
CN103013415B CN2012105817433A CN201210581743A CN103013415B CN 103013415 B CN103013415 B CN 103013415B CN 2012105817433 A CN2012105817433 A CN 2012105817433A CN 201210581743 A CN201210581743 A CN 201210581743A CN 103013415 B CN103013415 B CN 103013415B
Authority
CN
China
Prior art keywords
product
dmt
dimethyl terephthalate
melt adhesive
quality
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2012105817433A
Other languages
English (en)
Other versions
CN103013415A (zh
Inventor
李哲龙
朱万育
吴芳群
曾作祥
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunshan Tianyang New Material Co ltd
Tianyang New Material Shanghai Technology Co ltd
East China University of Science and Technology
Original Assignee
Shanghai Tianyang Hotmelt Adhesives Co ltd
KUNSHAN TIANYANG HOT MELT ADHESIVE CO LTD
East China University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Tianyang Hotmelt Adhesives Co ltd, KUNSHAN TIANYANG HOT MELT ADHESIVE CO LTD, East China University of Science and Technology filed Critical Shanghai Tianyang Hotmelt Adhesives Co ltd
Priority to CN2012105817433A priority Critical patent/CN103013415B/zh
Publication of CN103013415A publication Critical patent/CN103013415A/zh
Priority to US14/355,525 priority patent/US9346985B2/en
Priority to NZ623058A priority patent/NZ623058A/en
Priority to KR1020147014702A priority patent/KR101466677B1/ko
Priority to SG2014012892A priority patent/SG2014012892A/en
Priority to AU2013280006A priority patent/AU2013280006B2/en
Priority to PCT/CN2013/077547 priority patent/WO2013189294A1/zh
Application granted granted Critical
Publication of CN103013415B publication Critical patent/CN103013415B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

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

Abstract

本发明公开了一种半互穿网络结构型聚酯/聚乙烯醛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/乙二醛混合物，常温下搅拌使其混合均匀，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，具有剥离强度高、耐热性能好的特点。

Description

一种半互穿网络结构型聚酯/聚乙烯醛热熔胶及其制备工艺
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/聚乙烯醛热熔胶。 
技术背景
目前已知的聚酯热熔胶均采用二元酸酯和二元羧酸与二元醇依次经酯交换、酯化反应后，再经减压缩聚反应得到。如美国专利USP 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烯/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，如间苯二甲酸，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。 
本发明主要侧重于通过运用正交试验设计法确定最佳单体复配比例，以及在此基础上添加聚乙烯醇PVA/乙二醛混合物制备具有半互穿网络结构型的聚酯/聚乙烯醛热熔胶，此新型制备工艺制得的半互穿网络结构型的聚酯/聚乙烯醛热熔胶，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。 
因此，此产品具备优良的耐高温性能、耐干洗、耐水洗性能，且具有熔点低，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半互穿网络结构型的聚酯/聚乙烯醛热熔胶。 
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/聚乙烯醛热熔胶及其新型制备工艺，所制得的半互穿网络结构型的的聚酯/聚乙烯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。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。  
本发明的方法包括如下步骤： 
（1）将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，反应温度为140 ~ 180℃，气相温度保持在65 ~ 90℃， 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 ~ 1.5h，得共聚物粒子，再经冷冻，粉碎，可得共聚酯粉末； 
（3）在步骤（2）的产物中加入一定量的聚乙烯醇PVA/乙二醛混合物，常温下搅拌使其混合均匀，得目的产物。 
所述的其他二元酯为邻苯二甲酸二辛酯、1,6-己二酸二丁酯、1，10-癸二酸二丁酯、1,6-己二酸二甲酯、邻苯二甲酸二甲酯中的一种。 
所述的对苯二甲酸二甲酯与其他二元酯之间的摩尔比为1：0.2 ~ 0.35。 
所述的其他二元醇为乙二醇、1,6-己二醇、2,2,4-三甲基-1,3-戊二醇、新戊二醇，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之间的摩尔比为1 : 0.1 ~ 0.35； 
所述的总酯基和总羟基的摩尔比为1 : 1.1~1.8。 
所述的聚乙烯醇PVA/乙二醛混合物中，乙二醛的质量百分比为13.0% ~ 37.5%；该混合物的质量为步骤（2）的产物共聚酯质量的0.2% ~ 0.5% 。 
所述的有机锡催化剂为丁基锡酸，其用量为对苯二甲酸二甲酯质量的0.02% ~ 0.04%；所述的缩聚催化剂为钛酸四丁酯，其用量为对苯二甲酸二甲酯质量的0.02% ~ 0.04%。 
所述的稳定剂为亚磷酸三苯酯，其用量为对苯二甲酸二甲酯质量的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和乙二醛反应生成缩醛化合物，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/聚乙烯醛热熔胶。 
具体实施方法 
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，加入对苯二甲酸二甲酯291g，1,6-己二酸二甲酯87.1g，1,4-丁二醇225g，1,6-己二醇33.1g，2,2,4-三甲基-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℃左右时，开始有甲醇蒸馏出，恒定反应温度，待蒸出的甲醇达到理论量的95%以上时，酯化反应完成。保温0.5h，继续升温至220℃，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100Pa，反应时间30min，温度由220℃逐渐升高至235℃，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；在上述产物中加入聚乙烯醇PVA/乙二醛的混合物，该混合物中乙二醛的质量百分比为13.0%，混合物的质量为上述共聚酯质量的0.2%，常温下搅拌使其均匀，得热熔胶产品。分别用凝胶渗透色谱和DSC测定该产品平均分子量为15260g/mol , 熔点为：90-110℃，按国标GB/T3682-2000测得其熔体流动速率为：120g/10min160℃。 
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相关工艺参数和产物性能 
 实施例号 2 3 4 5 6
对苯二甲酸二甲酯，g 388.1  388.2  388.1  388.1  388.2 
邻苯二甲酸二辛酯，g 156.3         
1,6-己二酸二丁酯，g   116.6       
1,10-癸二酸二丁酯，g     94.2     
1,6-己二酸二甲酯，g       60.9   
邻苯二甲酸二甲酯，g         97.5 
1,4-丁二醇，g 189.1  288.2  243.8  261.6  324.2 
乙二醇, g 18.6    14.9  27.9   
1,6-己二醇, g   59.2      59.6 
2,2,4-甲基-1,3-戊二醇, g   90.5       
新戊二醇, g     31.2  46.8   
1,3-丙二醇, g 18.2        30.4
丁基锡酸, g 0.078  0.098  0.078 0.155  0.078 
亚磷酸三苯酯, g 0.12  0.122  0.349   0.14  0.039 
钛酸四丁酯，g 0.078 0.078 0.101  0.101   0.155 
酯化反应保温时间，min 30 40  45 50  60 
缩聚时间，min 40  50  65  60  70 
缩聚温度，℃ 200-220 220-240 220-250 220-240 220-245
PVA/乙二醛(23%)* : 共聚酯,   %   0.3   0.4  
PVA/乙二醛(31%)* : 共聚酯,   % 0.2   0.25    
PVA/乙二醛(37.5%)* : 共聚酯,  %         0.5
平均分子量 16200 21080 23090 25580 24890
熔点，℃ 98~112 104~116 102-109 105-115 104-122
熔融指数，g/10min(160℃) 95.7 88.3 84.7 83.2 81.9
* 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 (3)

1.一种半互穿网络结构型聚酯/聚乙烯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，反应温度为 140 ~ 180℃，气相温度保持在 65 ~ 90℃，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 ~ 1.5h，得共聚物粒子，再经冷冻，粉碎，得共聚物粉末 ；
（3）在步骤（2）的产物中加入一定量的聚乙烯醇 PVA/ 乙二醛混合物，常温下搅拌使其混合均匀，得目的产物 ；
所述的其他二元酯为邻苯二甲酸二辛酯、1,6- 己二酸二丁酯、1，10- 癸二酸二丁酯、1,6- 己二酸二甲酯、邻苯二甲酸二甲酯中的一种 ；
所述的对苯二甲酸二甲酯与其他二元酯之间的摩尔比为 1 ：0.2 ~ 0.35；
所述的其他二元醇为乙二醇、1,6- 己二醇、2,2,4- 三甲基 -1,3- 戊二醇、新戊二醇，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之间的摩尔比为 1 : 0.1 ~ 0.35；
所述的总酯基和总羟基的摩尔比为 1 : 1.1~1.8 ；
所述的聚乙烯醇 PVA/ 乙二醛混合物中，乙二醛质量百分比为 13% ~ 37.5%；该混合物的质量为步骤（2）的产物共聚酯质量的 0.2% ~ 0.5 %。
2.根据权利要求1所述的方法，其特征在于，所述的有机锡催化剂为丁基锡酸，其用量为对苯二甲酸二甲酯质量的0.02% ~ 0.04%；所述的缩聚催化剂为钛酸四丁酯，其用量为对苯二甲酸二甲酯质量的 0.02% ~ 0.04%。
3.根据权利要求1所述的方法，其特征在于，所述的稳定剂为亚磷酸三苯酯，其用量为对苯二甲酸二甲酯质量的 0.01% ~ 0.09%。
CN2012105817433A 2012-12-28 2012-12-28 一种半互穿网络结构型聚酯/聚乙烯醛热熔胶及其制备工艺 Active CN103013415B (zh)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CN2012105817433A CN103013415B (zh) 2012-12-28 2012-12-28 一种半互穿网络结构型聚酯/聚乙烯醛热熔胶及其制备工艺
US14/355,525 US9346985B2 (en) 2012-12-28 2013-06-20 Methods for preparation of polyester/glyoxalated polyvinyl alcohol semi-interpenetrating polymer network hot-melt adhesive
NZ623058A NZ623058A (en) 2012-12-28 2013-06-20 Preparation method for polyester/polyvinyl glyoxal hot melt adhesive having a semi-interpenetrating network structure
KR1020147014702A KR101466677B1 (ko) 2012-12-28 2013-06-20 반-상호침투 망상구조 폴리에스테르/폴리비닐　글리옥살　핫　멜트　접착제의 제조방법
SG2014012892A SG2014012892A (en) 2012-12-28 2013-06-20 Methods for preparation of polyester/glyoxalated polyvinyl alcohol semi-interpenetrating polymer network hot-melt adhesive
AU2013280006A AU2013280006B2 (en) 2012-12-28 2013-06-20 Preparation method for polyester/polyvinyl glyoxal hot melt adhesive having a semi-interpenetrating network structure
PCT/CN2013/077547 WO2013189294A1 (zh) 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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2012105817433A CN103013415B (zh) 2012-12-28 2012-12-28 一种半互穿网络结构型聚酯/聚乙烯醛热熔胶及其制备工艺

Publications (2)

Publication Number Publication Date
CN103013415A CN103013415A (zh) 2013-04-03
CN103013415B true CN103013415B (zh) 2013-12-04

Family

ID=47962540

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2012105817433A Active CN103013415B (zh) 2012-12-28 2012-12-28 一种半互穿网络结构型聚酯/聚乙烯醛热熔胶及其制备工艺

Country Status (7)

Country Link
US (1) US9346985B2 (zh)
KR (1) KR101466677B1 (zh)
CN (1) CN103013415B (zh)
AU (1) AU2013280006B2 (zh)
NZ (1) NZ623058A (zh)
SG (1) SG2014012892A (zh)
WO (1) WO2013189294A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103013415B (zh) * 2012-12-28 2013-12-04 昆山天洋热熔胶有限公司 一种半互穿网络结构型聚酯/聚乙烯醛热熔胶及其制备工艺
CN105348497B (zh) * 2015-12-07 2018-01-02 上海天洋热熔粘接材料股份有限公司 一种新型共聚酯热熔胶及其制备方法
CN106700362A (zh) * 2017-01-18 2017-05-24 彭先彧 一种具有耐水性的聚乙烯醇全生物降解薄膜及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3211688A (en) * 1961-04-20 1965-10-12 Wallace & Tiernan Inc Polyvinyl acetate plasticized with polyester
CN102492248A (zh) * 2011-12-09 2012-06-13 北京工商大学 用于聚丁二酸丁二醇酯及其共聚酯的大分子成核剂及应用方法
CN102575080A (zh) * 2009-08-07 2012-07-11 可乐丽股份有限公司 聚乙烯醇缩醛组合物、层叠体及其用途

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54154438A (en) * 1978-05-26 1979-12-05 Nippon Synthetic Chem Ind Co Ltd:The Production of high-viscosity polymer emulsion
US5904974A (en) * 1995-08-31 1999-05-18 Dainichiseika Color & Chemicals Mfg.Co., Ltd PVA-base thermoplastic copolymer and its production process and use
DE19831366A1 (de) 1998-07-13 2000-01-27 Inventa Ag Tiefschmelzende Copolyester- bzw. Copolyetheresterschmelzklebemassen
CN1138841C (zh) 2000-08-29 2004-02-18 上海理日科技发展有限公司 高熔点聚酯热熔胶的制造方法
CN101126006B (zh) 2007-06-29 2010-05-19 上海天洋热熔胶有限公司 一种聚酯热熔胶的制备方法
US8226022B2 (en) * 2010-07-28 2012-07-24 Eirich Machines, Inc. Mixer with a chopper
CN101955746B (zh) * 2010-10-15 2012-09-19 河海大学 一种高强复合金属材料用聚酯热熔胶的研制
CN102675609B (zh) * 2012-06-07 2013-09-18 昆山天洋热熔胶有限公司 一种快速结晶型纳米复合聚酯热熔胶及其制备工艺
CN103013415B (zh) * 2012-12-28 2013-12-04 昆山天洋热熔胶有限公司 一种半互穿网络结构型聚酯/聚乙烯醛热熔胶及其制备工艺

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3211688A (en) * 1961-04-20 1965-10-12 Wallace & Tiernan Inc Polyvinyl acetate plasticized with polyester
CN102575080A (zh) * 2009-08-07 2012-07-11 可乐丽股份有限公司 聚乙烯醇缩醛组合物、层叠体及其用途
CN102492248A (zh) * 2011-12-09 2012-06-13 北京工商大学 用于聚丁二酸丁二醇酯及其共聚酯的大分子成核剂及应用方法

Also Published As

Publication number Publication date
KR101466677B1 (ko) 2014-11-28
US9346985B2 (en) 2016-05-24
SG2014012892A (en) 2014-06-27
WO2013189294A1 (zh) 2013-12-27
NZ623058A (en) 2015-11-27
CN103013415A (zh) 2013-04-03
US20140303323A1 (en) 2014-10-09
AU2013280006A1 (en) 2014-07-17
AU2013280006B2 (en) 2015-01-29
KR20140091727A (ko) 2014-07-22

Similar Documents

Publication Publication Date Title
CN101724369B (zh) 一种高性能聚酯热熔胶的制备方法
CN105348497B (zh) 一种新型共聚酯热熔胶及其制备方法
US20140256875A1 (en) Process for preparing amorphous polyester hot melt adhesive with low melting point
CN102675609B (zh) 一种快速结晶型纳米复合聚酯热熔胶及其制备工艺
CN101245230A (zh) 线性共聚酯热熔胶的制备方法
CN103013415B (zh) 一种半互穿网络结构型聚酯/聚乙烯醛热熔胶及其制备工艺
CN103497316A (zh) 低端羧基含量的生物降解聚酯的制备方法
CN104558621A (zh) 一种连续制备低熔点共聚酰胺的方法
CN103483572B (zh) 一种低熔点耐水洗聚酯热熔胶的制备方法
CN103184027B (zh) 一种低粘度聚酯热熔胶及其制备方法
CN104109499B (zh) 一种难粘面料用聚酯热熔胶的制备方法
CN103468195A (zh) 一种生物可降解聚酯热熔胶的制备方法
CN102702698B (zh) 透明薄膜级pc/聚酯合金材料及其制备方法
CN104163913A (zh) 聚对苯二甲酸脂肪二酸丁二醇酯型共聚酯的制备方法
CN101469059A (zh) 一种阻燃共聚改性聚对苯二甲酸1,3-丙二醇酯的制备方法
CN103044671B (zh) 一种含二失水糖醇共聚酯的制备方法
CN112812725B (zh) 一种全生物降解压敏胶及其制备方法
KR102043372B1 (ko) 촉감과 색상이 우수한 저융점 바인더용 공중합 폴리에스테르 및 이를 이용한 폴리에스테르 바인더 복합섬유
CN103102647A (zh) 高热收缩率聚酯薄膜的制备方法
TW202208316A (zh) 塑化劑及其製造方法
CN104558553A (zh) 固相缩聚制备聚对苯二甲酸丙二醇酯的方法
KR20230067711A (ko) 아연 촉매를 이용한 폴리(트리메틸렌 퓨란디카복실레이트) 제조 공정
CN116496744A (zh) 一种熔体粘度低、固化快的聚酯热熔胶及制备方法
CN108264637A (zh) 一种基于1,2-丙二醇的高分子量聚酯酰胺树脂及其制备方法
CN108264636A (zh) 一种基于2,3-丁二醇的聚酯酰胺树脂及其制备方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee
CP01 Change in the name or title of a patent holder

Address after: Qiandeng Town Wenpu road Kunshan city Suzhou City, Jiangsu province 215341 No. 366

Patentee after: KUNSHAN TIANYANG HOT MELT ADHESIVE Co.,Ltd.

Patentee after: Shanghai Tianyang hot melt adhesive materials Limited by Share Ltd.

Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY

Address before: Qiandeng Town Wenpu road Kunshan city Suzhou City, Jiangsu province 215341 No. 366

Patentee before: KUNSHAN TIANYANG HOT MELT ADHESIVE Co.,Ltd.

Patentee before: Shanghai Tianyang Hotmelt Adhesives Co.,Ltd.

Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY

C56 Change in the name or address of the patentee
CP01 Change in the name or title of a patent holder

Address after: Qiandeng Town Wenpu road Kunshan city Suzhou City, Jiangsu province 215341 No. 366

Patentee after: KUNSHAN TIANYANG HOT MELT ADHESIVE Co.,Ltd.

Patentee after: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd.

Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY

Address before: Qiandeng Town Wenpu road Kunshan city Suzhou City, Jiangsu province 215341 No. 366

Patentee before: KUNSHAN TIANYANG HOT MELT ADHESIVE Co.,Ltd.

Patentee before: Shanghai Tianyang Hotmelt Adhesives Co.,Ltd.

Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY

CP03 Change of name, title or address

Address after: 215341 No. 366, Shipu Zhongjie Road, Qiandeng Town, Suzhou City, Jiangsu Province

Patentee after: Kunshan Tianyang New Material Co.,Ltd.

Patentee after: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd.

Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY

Address before: 215341 No. 366, Wenpu Road, Qiandeng Town, Kunshan City, Suzhou City, Jiangsu Province

Patentee before: KUNSHAN TIANYANG HOT MELT ADHESIVE Co.,Ltd.

Patentee before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd.

Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY

CP03 Change of name, title or address
CP01 Change in the name or title of a patent holder

Address after: 215341 No. 366, Shipu Zhongjie Road, Qiandeng Town, Suzhou City, Jiangsu Province

Patentee after: Kunshan Tianyang New Material Co.,Ltd.

Patentee after: Tianyang New Material (Shanghai) Technology Co.,Ltd.

Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY

Address before: 215341 No. 366, Shipu Zhongjie Road, Qiandeng Town, Suzhou City, Jiangsu Province

Patentee before: Kunshan Tianyang New Material Co.,Ltd.

Patentee before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd.

Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY

CP01 Change in the name or title of a patent holder