CN115124483B - 一种改性异氰酸酯及一种聚脲弹性体 - Google Patents
一种改性异氰酸酯及一种聚脲弹性体 Download PDFInfo
- Publication number
- CN115124483B CN115124483B CN202210625190.0A CN202210625190A CN115124483B CN 115124483 B CN115124483 B CN 115124483B CN 202210625190 A CN202210625190 A CN 202210625190A CN 115124483 B CN115124483 B CN 115124483B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- tributyl citrate
- isocyanate
- modified isocyanate
- polyurea elastomer
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/32—Cyanuric acid; Isocyanuric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/325—Polyamines containing secondary or tertiary amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/02—Polyureas
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开一种改性异氰酸酯及一种聚脲弹性体。所述改性异氰酸酯的结构式为
Description
技术领域
本发明涉及异氰酸酯和聚脲领域,具体涉及一种脂肪族异氰酸酯及制备的聚脲弹性体材料。
背景技术
HDI三聚体由于在三聚反应过程中存在副反应,产物中一般含有少量的HDI多聚体,平均分子量比理论值大,平均官能度通常在3~4之间。因此使用HDI三聚体制备的材料刚性大、硬度高,但材料较脆、柔韧性较差。
行业从业者常使用增塑剂来改善材料的脆性、柔韧性。因为增塑剂分子会***到聚合物分子链之间,增塑剂的极性基团会与聚合物极性基团相互作用,从而削弱了聚合物间的引力,降低了聚合物分子链间的缠结,从而使聚合物材料的塑性增加。
但增塑剂一般为小分子物质,在聚合物的高分子链间易于移动,在制品使用过程中,尤其是高温或承压的使用环境,增塑剂会逐渐从聚合物分子间迁移扩散至制品表面,导致制品出现发黄、***、变脆、表面油污、发粘、收缩等现象,影响制品使用性能及使用寿命。
发明内容
本发明的目的在于提供一种改性异氰酸酯。由其制备的聚脲制品具有良好的柔韧性、低温耐弯折性能等,并且可以避免使用增塑剂带来的负面效果。
为了实现以上技术目的,本发明采用以下技术方案:
本发明首先提供一种改性异氰酸酯,其结构式为:
本发明所述改性异氰酸酯的制备方法,包括以下步骤:在催化剂存在下,HDI三聚体与柠檬酸三丁酯反应。
反应式示意如下:
本发明所述制备方法中,HDI三聚体和柠檬酸三丁酯的质量比为2.0-4.0:1,优选2.2-3.8:1。
本发明所述制备方法中,所述HDI三聚体的平均官能度在3~4之间,NCO质量分数在22%左右,合适的例子包括但不限于万华化学的HT-100、HT-200、HT-300、HT-400、HT-500、HT-600等。
本发明所述制备方法中,所述柠檬酸三丁酯(TBC)纯度大于99.0%,酸度(以柠檬酸计)不大于0.02%,水分含量小于0.3%,合适的例子包括但不限于山东科兴TBC、广东佳信TBC等。
本发明所述制备方法中,所述催化剂选自新癸酸锌催化剂、新癸酸铋催化剂、二月桂酸二丁基锡、二(十二烷基硫)二丁基锡催化剂中的一种或多种。合适的例子包括但不限于美国领先的BiCAT8018、BiCAT Z,比利时优美科的Bi2010、Zn1910、Valikat14H2,赢创化学的Dabco T-120、Dabco T-12等。
本发明所述制备方法中,所述催化剂用量为反应物总质量的50-500ppm,优选80-450ppm。
本发明所述制备方法中,所述反应的温度为50-100℃,优选60-90℃。
第二个方面,本发明提供一种聚脲弹性体,包含以下重量份数的组分:
本发明所述聚天门冬氨酸树脂的平均官能度为2,平均分子量在400~600,合适的例子包括但不限于飞扬化工的F220、F420、F520、F2850等。
本发明所述胺类扩链剂的平均官能度为2,平均分子量在200~400,合适的例子包括但不限于万华化学的Wanalink6200和印度道夫凯特Unilink4100等。
本发明所述增塑剂选用环保型长链氯化石蜡(如山东岩海的52#氯化石蜡)、柠檬酸三丁酯(TBC)、乙酰基柠檬酸三丁酯(ATBC)、对苯二甲酸二辛酯(DOTP)、氯代棕榈油甲酯及环氧大豆油酸甲酯等中的一种或多种。
本发明所述固体填料选用碳酸钙、滑石粉、高岭土等中的一种或多种。
本发明所述多异氰酸酯包括本发明改性异氰酸酯和任选的脂肪族多异氰酸酯,其中本发明改性异氰酸酯用量占多异氰酸酯组分的质量比为10-100%,优选30-100%;脂肪族多异氰酸酯选自HDI三聚体、HDI缩二脲、脂肪族异氰酸酯预聚体等,合适的例子包括但不限于万华化学的HT-100、HT-200、HT-300、HT-400、HT-500、HT-600、HB-100以及IPDI预聚体等。
本发明所述的聚氨酯弹性体中,异氰酸酯指数为1.00~1.40,优选1.03~1.23。
一种制备本发明所述的聚脲弹性体的方法,包括以下步骤:聚天门冬氨酸树脂、胺类扩链剂、增塑剂、固体填料、多异氰酸酯加入到搅拌器内分散1~2min,然后将分散均匀的物料浇注到模具内,放置熟化。
本发明的有益效果包括:
(1)使用柠檬酸三丁酯化学改性HDI三聚体,可降低其官能度,从而降低制品的化学交联度,改善制品的脆性;
(2)使用柠檬酸三丁酯化学改性HDI三聚体,可引入柔性的酯类链段,从而改善制品的低温柔韧性;
(3)使用柠檬酸三丁酯化学改性HDI三聚体,对比常见的添加酯类增塑剂物理改性的方法,可避免增塑剂迁移导致的制品耐久性下降的问题;
(4)使用柠檬酸三丁酯化学改性HDI三聚体,对比常见的添加酯类增塑剂物理改性的方法,可明显改善制品耐高温性能。
附图说明
图1为实施例1产物的红外谱图。
图2为实施例1产物的核磁谱图。
具体实施方式
下面的实施例将对将对本发明所提供的方法予以进一步的说明,但本发明不限于所列出的实施例,还应包括在本发明的权利要求范围内其他任何公知的改变。
实施例1改性异氰酸酯A
将70.00g的柠檬酸三丁酯(广州佳信)加入到三口烧瓶中,加热至105℃真空除水2h。再降温至80℃,加入154.00g HDI三聚体(万华化学HT-100),反应2h后降温至70℃后滴加0.067g二月桂酸二丁基锡(赢创化学),反应6h后测试产物NCO含量11.35%,降温出料获得改性异氰酸酯A,反应过程中进行氮气保护。使用Nicolet iS5傅立叶变换红外光谱仪(美国Thermo fisher品牌)对上述产物进行测试,红外谱图见图1。采用Bruker AVANCEⅢ400Hz核磁共振波谱仪对产物进行碳谱分析,溶剂为CDCl3,结果如图2所示。
实施例2和对比例1、2、3聚脲弹性体制备
聚脲弹性体配方如下表1:
表1聚脲弹性体配方
实施例2 | 对比例1 | 对比例2 | 对比例3 | ||
原料 | 牌号/名称 | 重量份数 | 重量份数 | 重量份数 | 重量份数 |
天冬树脂 | F420 | 200 | 200 | 200 | 200 |
增塑剂 | 柠檬酸三丁酯 | 0 | 0 | 87 | 0 |
增塑剂 | 乙酰基柠檬酸三丁酯 | 0 | 0 | 0 | 62 |
异氰酸酯 | 改性异氰酸酯A | 279 | 0 | 0 | 0 |
异氰酸酯 | HT-100 | 0 | 145 | 192 | 145 |
异氰酸酯指数 | R | 1.05 | 1.05 | 1.05 | 1.05 |
按表1配方将各原料搅拌均匀后,使用刮膜器制备聚脲弹性体薄膜。置于恒温恒湿间养护7天后进行力学性能测试。
硬度按照《GB/T 531.1-2008》中第一部分的方法测试。拉伸强度按照《GB/T528》中对拉伸速度、样条形状的要求测试。
表2实施例2与对比例1、2、3聚脲弹性体薄膜各性能测试
测试项目 | 实施例2 | 对比例1 | 对比例2 | 对比例3 |
凝胶时间/min | 15 | 18 | 5 | 25 |
常温硬度 | 65A | 70D | 60A | 90A |
拉伸强度/MPa | 10.03 | 太脆,无法制样 | 8.04 | 36.10 |
断裂伸长率/% | 159 | 太脆,无法制样 | 177 | 16 |
-30℃低温弯折性 | 未开裂 | 开裂 | 未开裂 | 开裂 |
增塑剂是否析出 | 未析出 | —— | 略有析出 | 明显析出 |
80℃高温硬度保持率/% | 96.9% | —— | 92.1% | 88.7% |
由表2可知:
实施例2较对比例1,明显改善了制品的柔韧性以及低温弯折性。
实施例2较对比例2,对比例2中将等量的柠檬酸三丁酯一步法添加到配方体系中,使凝胶时间大幅缩短,施工性明显变差;且实施例2的拉伸强度以及高温硬度保持率明显优于对比例2。
实施例2配方体系中柠檬酸三丁酯占18%质量分数,按照此比例向对比例3中添加18%质量分数的不带有活泼氢基团的增塑剂乙酰基柠檬酸三丁酯。结果显示对比例3较实施例2,制品的柔韧性以及低温弯折性并没有得到明显改善;且对比例3还存在增塑剂析出和高温硬度保持率低的问题。
实施例3、4和对比例4、5、6
改性异氰酸酯B
将50.00g的柠檬酸三丁酯(广州佳信)加入到三口烧瓶中,加热至105℃真空除水2h。再降温至85℃,加入176.00g HDI三聚体(万华化学HT-300),反应2h后降温至80℃后滴加0.092g有机锌铋复合催化剂Valikat14H2(比利时优美科),反应8h后测试产物NCO含量13.01%,降温出料获得改性异氰酸酯B。反应过程中进行氮气保护。
制备异佛尔酮二异氰酸酯(IPDI)预聚体X,配方如下表:
表3IPDI预聚体X配方
组分 | 厂家 | 用量份数 |
聚醚多元醇F3135 | 万华化学 | 120 |
聚醚多元醇C2010 | 万华化学 | 100 |
1,4-丁二醇 | 阿拉丁 | 24 |
异佛尔酮二异氰酸酯IPDI | 万华化学 | 140 |
有机铋催化剂Bi2010 | 比利时优美科 | 0.03 |
按上述配方将聚醚多元醇F3135、C2010和1,4-丁二醇加入烧瓶中,105℃真空脱水2h,降温至80℃加入IPDI,反应1h后加入有机铋催化剂Bi2010,继续反应6h后降温至50℃出料,获得IPDI预聚体X,测试产物NCO含量为4.91%。
按照表4的配方制备聚脲弹性体。
表4聚脲弹性体配方
按表4配方将各原料搅拌均匀后,使用刮膜器制备聚脲弹性体薄膜。置于恒温恒湿间养护7天后进行力学性能测试。
硬度按照《GB/T 531.1-2008》中第一部分的方法测试。拉伸强度按照《GB/T 528》中对拉伸速度、样条形状的要求测试。
表5实施例3、4与对比例4、5、6聚脲弹性体薄膜各性能测试
测试项目 | 实施例3 | 实施例4 | 对比例4 | 对比例5 | 对比例6 |
常温硬度/A | 73 | 67 | 91 | 69 | 82 |
拉伸强度/MPa | 12.01 | 11.27 | 15.20 | 10.04 | 13.11 |
断裂伸长率/% | 160 | 182 | 67 | 179 | 81 |
-30℃低温弯折性 | 未开裂 | 未开裂 | 开裂 | 未开裂 | 开裂 |
增塑剂是否析出 | 未析出 | 略有析出 | —— | 略有析出 | 析出 |
80℃高温硬度保持率/% | 98.3 | 92.2 | —— | 94.3 | 89.2 |
由表5可知:
实施例3较对比例4,明显改善了制品的柔韧性以及低温弯折性。
实施例3较对比例5,实施例3的拉伸强度以及高温硬度保持率明显优于对比例5。
实施例3较对比例6,对比例6中加入增塑剂氯代棕榈油甲酯,没有明显改善制品的柔韧性以及低温弯折性,且带来增塑剂析出和高温硬度保持率低的问题。
实施例4较对比例6,实施例4中添加少量的增塑剂氯代棕榈油甲酯,即可使制品的柔韧性以及低温弯折性明显改善;且较对比例6,实施例4制品的增塑剂析出问题有所改善并具有更高的高温硬度保持率。
实施例5、6和对比例7、8、9
改性异氰酸酯C
将50.00g的柠檬酸三丁酯(广州佳信)加入到三口烧瓶中,加热至105℃真空除水2h。再降温至80℃,加入151.00g HDI三聚体(万华化学HT-600),反应2h后降温至75℃后滴加0.016g有机铋催化剂BiCAT8018(美国领先),反应7h后测试产物NCO含量14.03%,降温出料获得改性异氰酸酯C。反应过程中进行氮气保护。
制备异佛尔酮二异氰酸酯(IPDI)预聚体Y,配方如下表:
表7 IPDI预聚体Y配方
组分 | 厂家 | 用量份数 |
聚醚多元醇C2140 | 万华化学 | 200 |
聚醚多元醇C2020 | 万华化学 | 200 |
异佛尔酮二异氰酸酯IPDI | 万华化学 | 70 |
有机锡催化剂T12 | 赢创化学 | 0.04 |
按上述配方将聚醚多元醇C2140、C2020加入烧瓶中,105℃真空脱水2h,降温至70℃加入IPDI,反应1h后加入有机锡催化剂T12,继续反应8h后降温至50℃出料,获得IPDI预聚体Y,测试产物NCO含量为2.93%。
按照表8的配方制备聚脲弹性体。
表8聚脲弹性体配方
实施例5 | 实施例6 | 对比例7 | 对比例8 | 对比例9 | ||
原料 | 牌号/名称 | 重量份数 | 重量份数 | 重量份数 | 重量份数 | 重量份数 |
天冬树脂 | F420 | 120 | 120 | 120 | 120 | 120 |
胺类扩链剂 | Wanalink 6200 | 80 | 80 | 80 | 80 | 80 |
增塑剂 | 柠檬酸三丁酯 | 0 | 0 | 0 | 64 | 0 |
增塑剂 | 环氧大豆油酸甲酯 | 0 | 30 | 0 | 0 | 64 |
填料 | 400目滑石粉 | 180 | 180 | 180 | 180 | 180 |
异氰酸酯 | 改性异氰酸酯C | 254 | 254 | 0 | 0 | 0 |
异氰酸酯 | IPDI预聚体Y | 211 | 211 | 211 | 211 | 211 |
异氰酸酯 | HT-600 | 0 | 0 | 158 | 193 | 158 |
异氰酸酯指数 | R | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
按表8配方将各原料搅拌均匀后,使用刮膜器制备聚脲弹性体薄膜。置于恒温恒湿间养护7天后进行力学性能测试。
硬度按照《GB/T 531.1-2008》中第一部分的方法测试。拉伸强度按照《GB/T 528》中对拉伸速度、样条形状的要求测试。
表9实施例5、6与对比例7、8、9聚脲弹性体薄膜各性能测试
测试项目 | 实施例5 | 实施例6 | 对比例7 | 对比例8 | 对比例9 |
常温硬度/A | 52 | 47 | 71 | 48 | 62 |
拉伸强度/MPa | 5.88 | 5.36 | 7.59 | 4.82 | 6.93 |
断裂伸长率/% | 246 | 281 | 112 | 272 | 137 |
-30℃低温弯折性 | 未开裂 | 未开裂 | 开裂 | 未开裂 | 开裂 |
增塑剂是否析出 | 未析出 | 略有析出 | —— | 略有析出 | 析出 |
80℃高温硬度保持率/% | 95.2 | 89.0 | —— | 90.4 | 86.3 |
由表9可知:
实施例5较对比例7,明显改善了制品的柔韧性以及低温弯折性。
实施例5较对比例8,实施例5的拉伸强度以及高温硬度保持率明显优于对比例8。
实施例5较对比例9,对比例9中加入增塑剂环氧大豆油酸甲酯,没有明显改善制品的柔韧性以及低温弯折性,且带来增塑剂析出和高温硬度保持率低的问题。
实施例6较对比例9,实施例6中添加少量的增塑剂环氧大豆油酸甲酯,即可使制品的柔韧性以及低温弯折性明显改善;且较对比例9,实施例6制品的增塑剂析出问题有所改善并具有更高的高温硬度保持率。
Claims (8)
1.一种改性异氰酸酯,其结构式为:
2.制备权利要求1所述的改性异氰酸酯的方法,包括:在催化剂存在下,HDI三聚体与柠檬酸三丁酯反应。
3.根据权利要求2所述的方法,其特征在于,HDI三聚体和柠檬酸三丁酯的质量比为2.0-4.0:1。
4.根据权利要求2或3所述的方法,其特征在于,所述催化剂选自辛癸酸铋催化剂、辛癸酸锌催化剂、二月桂酸二丁基锡催化剂中的一种或多种。
5.根据权利要求4所述的方法,其特征在于,所述催化剂用量为反应物总质量的50-500ppm。
6.一种聚脲弹性体,包含以下重量份的组分:
其中,所述多异氰酸酯包括权利要求1-5任一项所述的改性异氰酸酯;
所述聚天门冬氨酸树脂的平均官能度为2,平均分子量在400~600;所述胺类扩链剂的平均官能度为2,平均分子量在200~400;
所述增塑剂选自长链氯化石蜡、柠檬酸三丁酯、乙酰基柠檬酸三丁酯、对苯二甲酸二辛酯、氯代棕榈油甲酯及环氧大豆油酸甲酯中的一种或多种;所述固体填料选用碳酸钙、滑石粉、高岭土中的一种或多种。
7.根据权利要求6所述的聚脲弹性体,其特征在于,所述多异氰酸酯任选地含有脂肪族多异氰酸酯,其中所述脂肪族多异氰酸酯选自HDI三聚体、HDI缩二脲、脂肪族异氰酸酯预聚体,其中,改性异氰酸酯占多异氰酸酯的质量比例为10-100%。
8.根据权利要求6-7任一项所述的聚脲弹性体,其特征在于,异氰酸酯指数为1.00~1.40。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210625190.0A CN115124483B (zh) | 2022-06-02 | 2022-06-02 | 一种改性异氰酸酯及一种聚脲弹性体 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210625190.0A CN115124483B (zh) | 2022-06-02 | 2022-06-02 | 一种改性异氰酸酯及一种聚脲弹性体 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115124483A CN115124483A (zh) | 2022-09-30 |
CN115124483B true CN115124483B (zh) | 2023-08-11 |
Family
ID=83378249
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210625190.0A Active CN115124483B (zh) | 2022-06-02 | 2022-06-02 | 一种改性异氰酸酯及一种聚脲弹性体 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115124483B (zh) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5070137A (en) * | 1988-07-22 | 1991-12-03 | Dainippon Ink And Chemicals, Inc. | Process for the preparation of polyisocyanate |
CN111057020A (zh) * | 2019-12-18 | 2020-04-24 | 万华化学集团股份有限公司 | 一种脂肪族异氰酸酯的叔胺改性物及其制备方法和光稳定聚氨酯泡沫 |
CN112794825A (zh) * | 2021-01-18 | 2021-05-14 | 马海社 | 一种柠檬酸酯增塑剂 |
CN112851592A (zh) * | 2021-01-18 | 2021-05-28 | 马海社 | 一种柠檬酸酯增塑剂及其制备方法 |
CN112940222A (zh) * | 2021-02-04 | 2021-06-11 | 万华化学(宁波)有限公司 | 一种絮凝稳定的多异氰酸酯组合物及其制备方法 |
CN114044869A (zh) * | 2021-12-02 | 2022-02-15 | 万华化学集团股份有限公司 | 一种仲胺类扩链交联剂及一种聚氨酯弹性材料 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10703933B2 (en) * | 2012-06-26 | 2020-07-07 | The Sherwin-Williams Company | Coreactants for polyurea coatings |
-
2022
- 2022-06-02 CN CN202210625190.0A patent/CN115124483B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5070137A (en) * | 1988-07-22 | 1991-12-03 | Dainippon Ink And Chemicals, Inc. | Process for the preparation of polyisocyanate |
CN111057020A (zh) * | 2019-12-18 | 2020-04-24 | 万华化学集团股份有限公司 | 一种脂肪族异氰酸酯的叔胺改性物及其制备方法和光稳定聚氨酯泡沫 |
CN112794825A (zh) * | 2021-01-18 | 2021-05-14 | 马海社 | 一种柠檬酸酯增塑剂 |
CN112851592A (zh) * | 2021-01-18 | 2021-05-28 | 马海社 | 一种柠檬酸酯增塑剂及其制备方法 |
CN112940222A (zh) * | 2021-02-04 | 2021-06-11 | 万华化学(宁波)有限公司 | 一种絮凝稳定的多异氰酸酯组合物及其制备方法 |
CN114044869A (zh) * | 2021-12-02 | 2022-02-15 | 万华化学集团股份有限公司 | 一种仲胺类扩链交联剂及一种聚氨酯弹性材料 |
Non-Patent Citations (1)
Title |
---|
新型聚脲涂层的制备及性能研究;孙德成等;《上海涂料》;第51卷(第04期);第12-14页 * |
Also Published As
Publication number | Publication date |
---|---|
CN115124483A (zh) | 2022-09-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109438653A (zh) | 一种生物型热塑性聚氨酯弹性体及其制备方法 | |
JPH0195119A (ja) | 熱可塑性ポリウレタン樹脂 | |
KR102291750B1 (ko) | 반응성 자외선 흡수제 및 이의 적용 | |
CN110352205B (zh) | 基于含氨基甲酸酯的聚合羟基化合物制备具有低起霜效应和良好的低温挠曲性的聚氨酯的方法 | |
EP1775313B1 (de) | Zusammensetzung zur Herstellung von Polyharnstoffbeschichtungen | |
CN110982027A (zh) | Cl-20***包覆用的聚氨酯组合物及其制备方法 | |
CN109608606A (zh) | 一种采矿车用聚氨酯实心轮胎的制备方法 | |
CN111004496A (zh) | 热塑性聚氨酯-氟硅橡胶弹性体及其制备方法 | |
JPH07103210B2 (ja) | 耐久性を有する熱可塑性ポリウレタン樹脂の製造方法 | |
CN115124483B (zh) | 一种改性异氰酸酯及一种聚脲弹性体 | |
CN112341593B (zh) | 一种汽车革用水性面层聚氨酯树脂及其制备方法 | |
CN108026233A (zh) | 热塑性聚氨酯 | |
CN109111891B (zh) | Htpb改性水性聚氨酯转移胶及其制备方法 | |
CN107652939B (zh) | 卷材用高粘性聚氨酯低硬度胶及其制备方法 | |
CN114106765B (zh) | 一种热塑性聚氨酯热熔胶及其制备方法 | |
EP0156950B1 (en) | A polyether derivative, a process for preparing the polyether derivative, a poly(urethane)ureamide obtained therefrom and a process for preparing the poly(urethane)ureamide | |
CN104193945A (zh) | 一种耐湿热水性聚氨酯树脂及其制备方法 | |
CN112552479B (zh) | 一种水解速度可控的无溶剂聚氨酯弹性体组合物 | |
CN104449540A (zh) | 用于pvc薄膜表面聚氨酯粘合剂组合物 | |
CN113754855A (zh) | 喷涂型聚氨酯弹性体组合物及其制备方法 | |
CN111793189A (zh) | 一种新型聚氨酯菜板材料及其制备方法 | |
JP4010006B2 (ja) | 熱可塑性ポリウレタン樹脂 | |
CN114957608B (zh) | 一种应用于输送带钢扣保护的聚氨酯胶粘剂及其制备方法 | |
CN117551415B (zh) | 一种聚氨酯胶黏剂及其制备方法 | |
CN117304676A (zh) | 高耐候的聚氨酯弹性体及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |