CN107531825A - 改性聚合物的方法 - Google Patents
改性聚合物的方法 Download PDFInfo
- Publication number
- CN107531825A CN107531825A CN201680022326.1A CN201680022326A CN107531825A CN 107531825 A CN107531825 A CN 107531825A CN 201680022326 A CN201680022326 A CN 201680022326A CN 107531825 A CN107531825 A CN 107531825A
- Authority
- CN
- China
- Prior art keywords
- functional group
- group
- maleimide
- polymer
- citraconimide
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene-diene terpolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
- C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/27—Compounds containing a nitrogen atom bound to two other nitrogen atoms, e.g. diazoamino-compounds
- C08K5/28—Azides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
- C08F222/402—Alkyl substituted imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
- C08F222/408—Imides, e.g. cyclic imides substituted imides comprising other heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/26—Elastomers
-
- 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
- C08J2307/00—Characterised by the use of natural rubber
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2323/36—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with nitrogen-containing compounds, e.g. by nitration
-
- 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
- C08J2325/00—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 aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- 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
- C08J2325/00—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 aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
- C08J2325/10—Copolymers of styrene with conjugated dienes
-
- 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
- C08J2331/00—Characterised by the use of 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 acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2331/04—Homopolymers or copolymers of vinyl acetate
-
- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
本发明涉及一种用于改性聚合物的方法,其包括以下步骤:(a)在处于80℃至250℃范围内的温度下将该聚合物与马来酰亚胺官能化的单叠氮化物和/或柠康酰亚胺官能化的单叠氮化物混合以形成经官能化的聚合物,和(b)使该经官能化的聚合物与含有一个或多个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质反应。
Description
本发明涉及一种使用(环)加成化学改性聚合物的方法。
弹性体常规地通过使用元素硫与若干种硫硫化促进剂组合来交联。然而,近几年来,用过氧化物交联的领域逐渐增加。与经硫交联的体系相比,过氧化物交联的优点为较好抗返硫性(reversion resistance)、较好耐热和耐化学性以及较好压缩变形。
因为不存在不饱和度,聚烯烃通常不采用基于硫的固化体系。此外,由于添加剂的褪色和硫组分的气味在聚烯烃应用中为高度不希望的。
聚乙烯通常用过氧化物来固化。然而,已知聚丙烯在过氧化物处理时降解。过氧化物用于通过形成长链支链而增强聚丙烯的熔体强度。
基于硫和过氧化物的交联均导致有机挥发物在交联方法期间且还由最终经交联的制品释放。可想象,在建筑和建造材料(例如窗户和门型材)中,挥发物由经交联的弹性体释放为不希望的。此外,固化体系的组分(即硫、促进剂、过氧化物和/或其分解产物)常常倾向于迁移至经处理的聚合物制品的表面(这称为喷出(blooming)或染色),其可能对皮肤或其他表面造成不希望的接触污染。
因此,将需要提供可在不释放有机挥发物和喷出/染色下进行的用于聚合物交联的方法。
该目的通过本发明的方法实现,其利用加成化学且可以使得氮气为所形成的唯一挥发物的方式进行。
该方法涉及在聚合物主链上引入马来酰亚胺和/或柠康酰亚胺基团。在该官能化期间,释放氮气。该方法的第二步骤涉及在所述马来酰亚胺和/或柠康酰亚胺基团与含有一个或多个可与马来酰亚胺或柠康酰亚胺基团反应的官能团的物质之间的反应。
该第二步骤优选涉及迈克尔加成或第尔斯-阿尔德环加成反应。如果所述物质仅含有一个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团,则聚合物由其他官能团改性;如果该物质含有两个或更多个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团,则将发生交联。所得交联潜在地为可逆的(逆第尔斯-阿尔德和逆迈克尔加成),其使如此交联的聚合物可再循环。
本发明的方法涉及一种用于改性聚合物的方法,其包括以下步骤:
a.在处于80℃至250℃范围内的温度下将所述聚合物与马来酰亚胺官能化的单叠氮化物和/或柠康酰亚胺官能化的单叠氮化物混合以形成经官能化的聚合物,和
b.使该经官能化的聚合物与含有一个或多个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质反应。
在一个优选实施方案中,在步骤b)中所用的物质含有至少两个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团,其导致聚合物交联。
因此,本发明还涉及一种交联聚合物的方法,其包括以下步骤:
a.在处于80℃至250℃范围内的温度下将所述聚合物与马来酰亚胺官能化的单叠氮化物和/或柠康酰亚胺官能化的单叠氮化物混合以形成经官能化的聚合物,和
b.使该经官能化的聚合物与含有至少两个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质反应。
本申请中的术语“聚合物”包括聚合物和低聚物。即其包括由至少2个,优选至少5个,最优选至少10个单体单元制成的材料。
可通过该方法合适地改性和/或交联的聚合物包括弹性体、链饱和聚合物、聚酯和这些聚合物中的一种或多种的共混物。
弹性体的实例为天然橡胶(NR)、苯乙烯丁二烯橡胶(SBR)、丁二烯橡胶(BR)、丁基橡胶(IIR)、乙烯丙烯共聚物弹性体(EPM)、乙烯丙烯二烯三元共聚物弹性体(EPDM)和乙烯乙酸乙烯酯共聚物(EVA)。
链饱和聚合物包括聚烯烃。合适聚烯烃为聚乙烯(LDPE、LLDPE、HDPE)和聚丙烯(PP)(其均聚物和共聚物二者)。该类共聚物的实例为聚烯烃弹性体(POE),其基于聚乙烯-辛烯或聚乙烯-丁烷共聚物。
聚酯的实例为聚乳酸(即聚交酯,PLA)和聚(羟基烷酸酯),如聚(羟基丁酸酯)、聚(琥珀酸亚丁酯)、聚乙醇酸交酯和聚(ε-己内酯)。
聚合物共混物的实例为热塑性聚烯烃(TPO)共混物、热塑性弹性体(TPE)共混物和TPV(EPDM/聚丙烯)共混物。
可用于本发明的方法中的马来酰亚胺官能化的单叠氮化物优选具有下式:
其中Y为
m为0或1,n为0或1,n+m=1或2,优选为1;
R选自:氢;任选地经含O、S、P、Si或N的官能团取代的具有1-6个碳原子的直链和支化烷基;具有1-6个碳原子的烷氧基;和卤素,且X为任选地含有杂原子的具有1-12个碳原子的直链或支化脂族或芳族烃结构部分。
可用于本发明的方法中的柠康酰亚胺官能化的单叠氮化物优选具有下式:
其中Y为
m为0或1,n为0或1,n+m=1或2,优选为1;R选自:氢;任选地经含O、S、P、Si或N的官能团取代的具有1-6个碳原子的直链和支化烷基;具有1-6个碳原子的烷氧基,和卤素,且X为任选地含有杂原子的具有1-12个碳原子的直链或支化脂族或芳族烃结构部分。
在上式中,R优选为氢。
当上式中的X含有杂原子时,其优选具有以下结构中的一个:
其中P为处于1至6范围内的整数,且R选自:H、烷基、芳基、苯基和经取代的苯基。
然而,更优选地,X为具有1-12个,更优选1-6个,最优选2-4个碳原子的脂族烷二基。
尤其优选的马来酰亚胺官能单叠氮化物为4-(2,5-二氧代-2,5-二氢-1H-吡咯-1-基)苯磺酰基叠氮化物:
尤其优选的柠康酰亚胺官能单叠氮化物为
即分别为4-(3-甲基-2,5-二氧代-2,5-二氢-1H-吡咯-1-基)苯磺酰基叠氮化物(还称为柠康酰亚胺苯磺酰基叠氮化物)和叠氮甲酸2-(3-甲基-2,5-二氧代-2,5-二氢-1H-吡咯-1-基)乙酯(还称为柠康酰亚胺-C2-叠氮基甲酸酯)。
官能化步骤a)可在能够在80℃至250℃范围内的温度下混合聚合物的任何合适设备中进行。该类设备的实例为内部分批混合器(常常称为Banbury混合器)、双辊磨机(条件为辊可加热)、挤出机等。官能化的结果为含有马来酰亚胺和/或柠康酰亚胺官能团的聚合物。
优选将经官能化的叠氮化物以0.01-20phr,更优选0.05-10phr,最优选0.1-5phr的量与聚合物混合。术语“phr”意指:每一百重量份聚合物的重量份。
除聚合物和经官能化的叠氮化物以外,还可向混合物中添加自由基清除剂和抗氧化剂。自由基清除剂的实例为叔丁基氢醌(TBHQ)、2,2,6,6-四甲基哌啶氧基(TEMPO)和4-羟基-2,2,6,6-四甲基哌啶-1-氧基(OH-TEMPO)。合适抗氧化剂的实例为位阻多核酚类(例如SKF、DS、Vulkanox BKF、Irganox 1010)、胺类抗氧化剂(例如Flectol TMQ)、基于二苯基二胺的抗氧化剂(例如Santonox 6PPD)和亚磷酸酯(例如WestonTNPP)。
官能化在处于80℃至250℃,优选90℃至230℃,更优选100℃至200℃,最优选110℃至180℃范围内的温度下进行。所选温度取决于聚合物类型和叠氮化物类型。
在该官能化反应期间,形成N2。
磺酰基叠氮化物(叠氮基磺酸酯)通常在约130℃开始分解成反应性氮宾(nitrene)物质,峰值在约180℃;叠氮基甲酸酯在高于110℃下开始分解,且峰值在160℃。所形成的氮宾结构部分与聚合物反应,使得氮宾接枝至聚合物上。
叠氮化物可与不饱和聚合物反应的另一种机理经由所谓的“点击(click)”机理,其可在低于叠氮化物的分解温度下发生。在完全饱和的聚合物上,该“点击”机理将不会发生。
优选反应时间为1-120分钟,更优选为1-60分钟,最优选为2-30分钟。
使经官能化的聚合物与含有一个或多个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质反应。
该反应可为迈克尔加成反应或第尔斯-阿尔德环加成反应。在一个优选实施方案中,在官能化步骤a)之后向经官能化的聚合物中添加该物质。然而,当反应根据第尔斯-阿尔德环加成机理进行时,还可在官能化步骤a)之前或之中向该聚合物中添加该物质。
官能团优选选自胺、硫醇、呋喃和山梨酸酯基团。胺和硫醇经由迈克尔加成与马来酰亚胺和柠康酰亚胺官能团反应;呋喃和山梨酸酯酯基团经由第尔斯-阿尔德环加成反应。
仅含有一个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团且可适合用于改性聚合物的特性(例如改进与极性填料的相互作用)的物质的实例为氨基醇、氨基酸、聚醚单胺(Jeffamines)、呋喃、氨基官能硅烷、巯基酸和巯基醇。
氨基醇的实例为具有伯氨基团的氨基醇,例如乙醇胺、丙醇胺、丁醇胺等。
呋喃的实例为糠基醇(furfurylalcohol)、甲基丙烯酸糠基酯、糠基缩水甘油醚和糠基异氰酸酯。
氨基官能硅烷的实例为(3-氨基丙基二异丙基乙氧基硅烷、3-氨基丙基二甲基乙氧基硅烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基-硅烷、N-(2-氨基乙基)-3-氨基丙基三乙氧基硅烷、N-(6-氨基己基)氨基甲基三乙氧基硅烷、N-(6-氨基己基)氨基丙基三甲氧基硅烷、N-(2-氨基乙基)-11-氨基十一烷基三甲氧基硅烷、(氨基乙基氨基甲基)苯乙基三甲氧基硅烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-(2-氨基乙基)-3-氨基异丁基甲基二甲氧基硅烷、(氨基乙基氨基)-3-异丁基二甲基甲氧基硅烷和(3-三甲氧基甲硅烷基丙基)二亚乙基三胺)。
硫醇的实例为3-巯基丙酸、1-巯基-2-丙醇、3-巯基-1-丙醇、4-巯基-1-丁醇、6-巯基己酸、6-巯基-1-己醇、6-巯基-1-己醇、8-巯基辛酸、8-巯基-1-辛醇、9-巯基-1-壬醇、11-巯基十一烷酸、11-巯基十一烷酸、11-巯基十一烷酰胺、11-叠氮基-1-十一烷硫醇、11-巯基-1-十一烷醇、11-巯基-1-十一烷醇、11-巯基十一烷基膦酸、11-巯基十一烷基膦酸、12-巯基十二烷酸、12-巯基十二烷酸、11-(1H-吡咯-1-基)十一烷-1-硫醇、12-巯基十二烷酸NHS酯、16-巯基十六烷酸、16-巯基十六烷酸、三乙二醇单-11-巯基十一烷基醚、(11-巯基十一烷基)四(乙二醇)和(11-巯基十一烷基)六(乙二醇)。
优选硫醇为3-巯基丙酸、1-巯基-2-丙醇、3-巯基-1-丙醇、4-巯基-1-丁醇、6-巯基己酸和6-巯基-1-己醇。
与聚合物的相互作用可由于该方法而改进的填料的实例为碳黑、二氧化硅、硅酸盐、云母、氧化铝、氢氧化物(如氢氧化镁和氢氧化铝)、碳酸盐(如碳酸钙)、粘土、纳米粘土、硫酸盐(如硫酸钡)和具有极性特征的天然有机填料(如木材或木质素纤维、纤维素纤维和大麻)。
如果物质含有两个或更多个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团,则该两个或更多个官能团优选选自胺、硫醇、呋喃和山梨酸酯基团。至少两个官能团可相同或不同。
具有至少两个硫醇基的物质的实例包括具有三个巯基的物质,例如1,2,6-己三醇三巯基乙酸酯、1,3,5-三聚硫氰酸、三羟甲基丙烷三(3-巯基丙酸酯)或三羟甲基丙烷三巯基乙酸酯;和具有四个或更多个巯基的物质,例如季戊四醇四(3-巯基丙酸酯)、季戊四醇四巯基乙酸酯、季戊四醇六(3-巯基丙酸酯)或季戊四醇六巯基乙酸酯。
具有至少两个氨基的物质的实例包括双(六亚甲基)三胺、1,6-二氨基己烷、异佛尔酮二胺、三(2-氨基乙基)胺、4-氨基苯基醚、1,2-二氨基丁烷、1,4-二氨基丁烷、1,5-二氨基戊烷、1,5-二氨基(2甲基)戊烷、1,7-二氨基庚烷、1,8-二氨基辛烷、1,9-二氨基壬烷、1,10-二氨基癸烷、1,12-二氨基十二烷、1,6-二氨基-(2,2,3-三甲基)己烷、三环十二烷二胺、间苯二甲基二胺、(邻-间-和对-)二氨基苯(苯二胺)、2,2'-二硫基双(乙胺)、二苯胺甲烷、二苯胺醚、二苯胺砜、2,2',6,6'-四乙基二苯胺甲烷、2,2',6,6'-四甲基二苯胺甲烷、2,2'-二甲基-6,6'-二乙基二苯胺甲烷、2,2',6,6'-四-异丙基二苯胺甲烷、2,2'-二异丙基-6,6'-二甲基二苯胺甲烷、1,8-二氨基-薄荷烷、4-氨基甲基-1,8-辛烷二胺、N-苯基-1,4-苯二胺、4,4'二苯胺基二苯胺、1,8-二氨基-3,6-二氧杂辛烷、1,5-二氨基-3-氧杂戊烷、α,ω-聚四氢呋喃基二胺、α,ω-聚乙二醇二胺α,ω-聚丙氧基二胺α,ω-聚乙氧基-丙氧基二胺、3,5-二氨基苯甲酸、3,4-二氨基二苯甲酮、1,2-二氨基环己烷、二氨基萘和二氨基甲苯。
优选多官能胺为双(六亚甲基)三胺、1,6-二氨基己烷、异佛尔酮二胺、三(2-氨基乙基)胺和4-氨基苯基醚。
具有胺和硫醇基的物质的实例包括3-氨基-1-丙硫醇盐酸盐、6-氨基-1-己硫醇盐酸盐、8-氨基-1-辛硫醇盐酸盐、11-氨基-1-十一烷硫醇盐酸盐和16-氨基-1-十六烷硫醇盐酸盐。
具有两个或更多个经由第尔斯-阿尔德环加成与马来酰亚胺和柠康酰亚胺基团反应的官能团的物质的实例包括2,2-二(2-呋喃基)丙烷、硫代二亚甲基二呋喃和乙烷-1,2-二基(2E,2'E,4E,4'E)-双(己-2,4-二烯酸酯)。
可在分子一侧经由第尔斯-阿尔德环加成反应且在另一侧经由迈克尔加成反应的物质的实例为糠基胺和糠基硫醇。
含有一个或多个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质优选以0.1-3.0,更优选0.2-2.0,最优选地0.5-1.5的摩尔当量比添加至经官能化的聚合物中。术语“摩尔当量比”是指相对于马来酰亚胺和柠康酰亚胺基团的总数的可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的总数。
含有一个或多个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质可使用例如双辊磨机或挤出机混合至经官能化的聚合物中。混合可在室温下或在允许在不过早交联下混合的任何其他温度下进行。优选温度范围为20℃至40℃。
可添加催化剂从而加速加成反应,但这并非必需的。如果物质含有硫醇官能团,则优选添加碱催化剂。合适催化剂的实例包括1,4-二氮杂双环[2.2.2]辛烷(DABCO)、三乙胺、奎宁环醇(quinuclidinol)、三苯基膦和氢氧化物。
如果含有一个或多个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质含有脂族胺官能团,则不需要催化剂;而如果该物质含有芳族胺官能团,则可添加酸催化剂,例如乙酸。
第尔斯-阿尔德环加成不需要任何催化剂。
任选地催化剂可以基于经官能化的聚合物的重量0.01-2.0wt%,更优选0.02-1.0wt%,最优选地0.05-0.50wt%的浓度添加至经官能化的聚合物中。
所得混合物可以所需形式成形。该成形可在塑模(压缩模塑、注射模塑或传递模塑)、挤出机(其中成形模具可安装在挤出机顶部)或砑光机(以将聚合物熔体加工成片材或薄膜)中进行。此外,所谓的热成形方法可用于由聚烯烃箔片或片材成形为形状。
可随后在处于40℃至250℃,优选45℃至200℃,最优选地50℃至190℃范围内的温度下对经成形的混合物进行热处理从而使交联反应发生。
通过本发明的方法可获得的经交联的聚合物可在许多应用中用作使用硫固化促进剂或过氧化物交联的聚合物的替代物,这些应用包括建筑和建造材料(窗户和门型材)、电线和电缆应用、轮胎(侧壁、胎面)、(传送机)带、气囊、软管、管、密封件、手套、对接挡板、鞋类、地板和自动扶梯扶手。
实施例
实施例1
用柠康酰亚胺苯磺酰基叠氮化物使无不饱和度的乙烯-丙烯共聚物(EPM,购自Exxon Mobil的VistalonTM 404)官能化。为实现该官能化,将47克EPM与0.93克柠康酰亚胺苯磺酰基叠氮化物混合,且在Banbury型内部混合器中在150℃至180℃下热处理20分钟以使叠氮化物接枝至EPM上。
向所得经官能化的EPM中添加季戊四醇四(3-巯基丙酸酯)和0.1wt%催化剂DABCO(1,4二氮杂双环[2.2.2]辛烷,还称为三亚乙基二胺),且在双辊磨机上在处于20℃至40℃之间的温度下混合这些物质。所添加的季戊四醇四(3-巯基丙酸酯)的量基于总混合物对应于1.1wt%,且柠康酰亚胺官能团与四硫醇的摩尔比为3:1。
通过使用Alpha Technologies MDR2000流变仪在170℃下使样品固化30分钟来测试固化速度和交联性能。根据ISO 6502-1991(用无转子固化仪测量硫化特征)分析结果。
固化时间(t90;实现最终最大交联密度的90%所需的时间)为15分钟。表示最终交联密度Δ转矩(ΔS)为0.23Nm。
实施例2
重复实施例1,不同的是:
-使用马来酰亚胺苯磺酰基叠氮化物代替柠康酰亚胺苯磺酰基叠氮化物,
-使用0.2wt%DABCO,
-不使用或使用0.8wt%季戊四醇四(3-巯基丙酸酯)(使得马来酰亚胺官能团与四硫醇的摩尔比为约4:1),且
-聚合物在180℃而非170℃下进行交联。
结果列于表1中。
表1
表2列出用所示量的交联剂(四硫醇)改性的EPM的交联性能。列出的为t90,即获得最终最大交联密度90%所需的时间,和在流变仪中所测量的Δ转矩ΔS。实验清楚地显示出交联反应发生需要四硫醇。
实施例3
用马来酰亚胺苯磺酰基叠氮化物官能化乙烯-丙烯二烯三元共聚物(EPDM,购自Lanxess Elastomers的Keltan 5470C)。为实现该官能化,将50克EPDM与1克马来酰亚胺苯磺酰基叠氮化物和1克SKF(防止凝胶形成的稳定剂,由此改进可加工性)混合,且在Banbury型内部混合器中在120℃至170℃下热处理25分钟以使叠氮化物接枝至EPDM上。
在官能化之后,使用双辊磨机在20℃至40℃下向经改性的EPDM中添加1当量硫代二亚甲基二呋喃。马来酰亚胺官能团与双呋喃交联剂的摩尔比为2:1。
交联通过将所得混合物在150℃下加热5分钟且在50℃下再加热24小时来进行。这允许第尔斯-阿尔德交联反应进行。
表2显示出用于官能化的配方(第3A项)和使用双呋喃交联经官能化的EPDM。
实施例3B-3D为对比例,其显示出起始EPDM(3B)和用不同量的过氧化二异丙苯交联的EPDM(3C和3D)的交联密度。样品3C和3D通过加热至170℃并保持30分钟以使过氧化物充分分解为有效自由基来进行交联。
交联密度使用甲苯中的平衡溶胀方法和在交联密度与以实验方式测定的经溶胀的样品中橡胶体积分数(φ)之间的Flory-Rehner关系来测量。EPDM与甲苯的组合使用Flory-Huggins相互作用参数0.429+0.218φ。
表2中的结果表明EPDM本身不显示出交联密度,而利用本发明的第尔斯-阿尔德交联体系交联的EPDM的交联密度与用0.2-0.4phr过氧化物(过氧化二异丙苯)交联的EPDM相当。
表2
*未交联的EPDM完全溶解于甲苯中。
实施例4
用柠康酰亚胺苯磺酰基叠氮化物官能化丁基橡胶(BR,RubberBR40)。为实现该官能化,将47克BR与0.94克柠康酰亚胺苯磺酰基叠氮化物混合,且在Banbury型内部混合器中在150℃至180℃下热处理20分钟以使叠氮化物接枝至BR上。
向所得经官能化的BR中添加0.24克乙醇胺,且将物质在双辊磨机上在处于20℃至40℃之间的温度下混合。柠康酰亚胺官能团与乙醇胺的摩尔比为约1:1。
在1H-NMR光谱(使用CDCl3作为溶剂)中,游离乙醇胺在2.8和3.6ppm处给出信号。在以上处理之后,这些信号分别移动至3.1和3.7ppm。1D-DOSY NMR显示出,3.1和3.7ppm处的这些信号属于高分子量部分,其证明乙醇胺连接至丁基橡胶。
Claims (16)
1.一种用于改性聚合物的方法,包括以下步骤:
a.在处于80℃至250℃范围内的温度下将所述聚合物与马来酰亚胺官能化的单叠氮化物和/或柠康酰亚胺官能化的单叠氮化物混合以形成经官能化的聚合物,和
b.使所述经官能化的聚合物与含有一个或多个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质反应。
2.根据权利要求1的方法,其中所述物质含有至少两个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团。
3.根据权利要求1或2的方法,其中所述经官能化的聚合物与所述含有一个或多个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质之间的反应涉及迈克尔加成反应或第尔斯-阿尔德环加成反应。
4.根据权利要求1-3中任一项的方法,其中所述一个或多个官能团选自胺、硫醇、呋喃和山梨酸酯基团。
5.根据权利要求1和3-4中任一项的方法,其中所述含有至少两个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质选自由如下组成的组:氨基醇、氨基酸、聚醚单胺(Jeffamines)、呋喃、氨基官能硅烷、巯基酸和巯基醇。
6.根据权利要求2-4中任一项的方法,其中所述含有至少两个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质选自由如下组成的组:1,2,6-己三醇三巯基乙酸酯、1,3,5-三聚硫氰酸、三羟甲基丙烷三(3-巯基丙酸酯)、三羟甲基丙烷三巯基乙酸酯、季戊四醇四(3-巯基丙酸酯)、季戊四醇四巯基乙酸酯、季戊四醇六(3-巯基丙酸酯)和季戊四醇六巯基乙酸酯。
7.根据权利要求2-4中任一项的方法,其中所述含有至少两个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质选自由如下组成的组:双(六亚甲基)三胺、1,6-二氨基己烷、异佛尔酮二胺、三(2-氨基乙基)胺、4-氨基苯基醚、双(六亚甲基)三胺和三(2-氨基乙基)胺。
8.根据权利要求2-4中任一项的方法,其中所述含有至少两个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质选自由如下组成的组:2,2-二(2-呋喃基)丙烷、二糠基硫化物、2,2-二(2-呋喃基)丙烷、硫代二亚甲基二呋喃和乙烷-1,2-二基(2E,2'E,4E,4'E)-双(己-2,4-二烯酸酯)。
9.根据权利要求2-4中任一项的方法,其中所述含有至少两个可与马来酰亚胺或柠康酰亚胺官能团反应的官能团的物质选自由如下组成的组:季戊四醇四(3-巯基丙酸酯)、双(六亚甲基)三胺、三(2-氨基乙基)胺、2,2-二(2-呋喃基)丙烷和二糠基硫化物。
10.根据前述权利要求中任一项的方法,其中所述聚合物为弹性体。
11.根据权利要求10的方法,其中所述弹性体选自由如下组成的组:天然橡胶(NR)、苯乙烯丁二烯橡胶(SBR)、丁二烯橡胶(BR)、丁基橡胶(IIR)、乙烯丙烯共聚物弹性体(EPM)、乙烯丙烯二烯三元共聚物弹性体(EPDM)和乙烯乙酸乙烯酯共聚物(EVA)。
12.根据权利要求1-9中任一项的方法,其中所述聚合物为聚烯烃。
13.根据权利要求12的方法,其中所述聚烯烃选自由如下组成的组:聚乙烯、聚丙烯和聚烯烃弹性体。
14.根据前述权利要求中任一项的方法,其中所述马来酰亚胺官能化的叠氮化物具有以下结构:
其中Y为
m为0或1,n为0或1,n+m=1或2;R选自由如下组成的组:氢;任选地经含O、S、P、Si或N的官能团取代的具有1-6个碳原子的直链和支化烷基;具有1-6个碳原子的烷氧基;和卤素,且X为任选地含有杂原子的具有1-12个碳原子的直链或支化脂族或芳族烃结构部分。
15.根据前述权利要求中任一项的方法,其中所述柠康酰亚胺官能化的叠氮化物具有以下结构:
其中Y为
m为0或1,n为0或1,n+m=1或2;R选自由如下组成的组:氢;任选地经含O、S、P、Si或N的官能团取代的具有1-6个碳原子的直链和支化烷基;具有1-6个碳原子的烷氧基;和卤素,且X为任选地含有杂原子的具有1-12个碳原子的直链或支化脂族或芳族烃结构部分。
16.根据前述权利要求中任一项的方法,其中所述单叠氮化物选自由如下组成的组:4-(2,5-二氧代-2,5-二氢-1H-吡咯-1-基)苯磺酰基叠氮化物、4-(3-甲基-2,5-二氧代-2,5-二氢-1H-吡咯-1-基)苯磺酰基叠氮化物(还称为柠康酰亚胺苯磺酰基叠氮化物)和叠氮甲酸2-(3-甲基-2,5-二氧代-2,5-二氢-1H-吡咯-1-基)乙酯(还称为柠康酰亚胺-C2-叠氮基甲酸酯)。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15165044.7 | 2015-04-24 | ||
EP15165044 | 2015-04-24 | ||
PCT/EP2016/058822 WO2016170018A1 (en) | 2015-04-24 | 2016-04-21 | Process for modifying polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107531825A true CN107531825A (zh) | 2018-01-02 |
Family
ID=53015568
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201680022326.1A Withdrawn CN107531825A (zh) | 2015-04-24 | 2016-04-21 | 改性聚合物的方法 |
Country Status (12)
Country | Link |
---|---|
US (1) | US10093762B2 (zh) |
EP (1) | EP3286253A1 (zh) |
JP (1) | JP2018517796A (zh) |
KR (1) | KR20170135937A (zh) |
CN (1) | CN107531825A (zh) |
AR (1) | AR104351A1 (zh) |
BR (1) | BR112017022100A2 (zh) |
MX (1) | MX2017013392A (zh) |
RU (1) | RU2017134782A (zh) |
SG (1) | SG11201708227WA (zh) |
TW (1) | TW201704272A (zh) |
WO (1) | WO2016170018A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110624204A (zh) * | 2019-08-29 | 2019-12-31 | 青岛三鸿塑料制品有限公司 | 一种防滑性能好的空手道训练垫及其制造工艺 |
CN116396434A (zh) * | 2023-03-13 | 2023-07-07 | 天津大学 | 基于功能化接枝改性提升聚丙烯薄膜高温击穿性能的方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018513257A (ja) | 2015-04-24 | 2018-05-24 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップAkzo Nobel Chemicals International B.V. | ポリマーを官能化する方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101360769A (zh) * | 2005-03-17 | 2009-02-04 | 陶氏环球技术公司 | 官能化的乙烯/α-烯烃嵌段共聚体组合物 |
CN102143980A (zh) * | 2008-07-03 | 2011-08-03 | 株式会社普利司通 | 用含被保护氨基的酰亚胺化合物官能化的聚合物 |
CN103180352A (zh) * | 2010-09-21 | 2013-06-26 | W.L.戈尔及同仁股份有限公司 | 可膨胀的官能化tfe共聚物细粉末、由其制得的膨胀的官能化制品以及膨胀的制品的反应 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3137745A (en) | 1962-10-15 | 1964-06-16 | Hercules Powder Co Ltd | Method of forming hollow plastic articles |
US3205206A (en) | 1962-10-15 | 1965-09-07 | Hercules Powder Co Ltd | Modifying polymers |
US4352938A (en) | 1969-07-18 | 1982-10-05 | Hercules Incorporated | Epoxy-azidoformate compounds |
US3631182A (en) | 1970-05-21 | 1971-12-28 | Hercules Inc | Aliphatic bis(azidoformate)s |
DE2919823A1 (de) * | 1979-05-16 | 1980-11-20 | Siemens Ag | N-azidosulfonylaryl-maleinimide sowie deren verwendung |
DE2919841A1 (de) | 1979-05-16 | 1980-11-20 | Siemens Ag | Verfahren zur phototechnischen herstellung von reliefstrukturen |
DE3342851A1 (de) | 1983-11-26 | 1985-06-05 | Merck Patent Gmbh, 6100 Darmstadt | Fotolacke |
DE69528941T2 (de) | 1994-09-19 | 2003-09-18 | Sentinel Products Corp | Vernetzte Schaumstrukturen von hauptsächlich linearen Polyolefinen und Verfahren zur Herstellung |
US5844049A (en) | 1994-12-28 | 1998-12-01 | Akzo Nobel Nv | Sulfur-vulcanized rubber compositions comprising substituted succinimide compounds |
TWI287536B (en) | 2000-04-18 | 2007-10-01 | Ind Tech Res Inst | Method for preparing azide photo-initiators |
US20030044468A1 (en) | 2001-03-20 | 2003-03-06 | Francesco Cellesi | Two-phase processing of thermosensitive polymers for use as biomaterials |
ES2445946T3 (es) | 2003-08-14 | 2014-03-06 | Akzo Nobel Coatings International B.V. | Pintura que comprende una fase líquida y una fase de polvo activo |
JP4372662B2 (ja) | 2004-10-26 | 2009-11-25 | 株式会社神戸製鋼所 | 形状検出装置及び形状検出プログラム |
US20090275703A1 (en) | 2005-12-20 | 2009-11-05 | Stichting Dutch Polymer Institute | Process for cross-linking copolymers using a sulfur-containing co-agent |
US8063161B2 (en) | 2007-04-16 | 2011-11-22 | Designer Molecules, Inc. | Low temperature curing acrylate and maleimide based formulations and methods for use thereof |
US9388276B2 (en) | 2011-02-25 | 2016-07-12 | University Of Massachusetts | Monomers and polymers for functional polycarbonates and poly(ester-carbonates) and PEG-co-polycarbonate hydrogels |
MX2016005599A (es) * | 2013-11-07 | 2016-07-21 | Akzo Nobel Chemicals Internac B V | Proceso para modificar polimeros y copolimeros a base de etileno. |
TR201802194T4 (tr) | 2013-11-07 | 2018-03-21 | Akzo Nobel Chemicals Int Bv | Siklik karbonat azit. |
WO2015067531A1 (en) | 2013-11-07 | 2015-05-14 | Akzo Nobel Chemicals International B.V. | Process for modifying polymers |
JP2018513257A (ja) | 2015-04-24 | 2018-05-24 | アクゾ ノーベル ケミカルズ インターナショナル ベスローテン フエンノートシャップAkzo Nobel Chemicals International B.V. | ポリマーを官能化する方法 |
SG11201708225SA (en) | 2015-04-24 | 2017-11-29 | Akzo Nobel Chemicals Int Bv | Process for crosslinking polypropylene |
-
2016
- 2016-04-21 KR KR1020177032347A patent/KR20170135937A/ko active IP Right Grant
- 2016-04-21 BR BR112017022100A patent/BR112017022100A2/pt not_active IP Right Cessation
- 2016-04-21 US US15/567,090 patent/US10093762B2/en not_active Expired - Fee Related
- 2016-04-21 EP EP16721695.1A patent/EP3286253A1/en not_active Withdrawn
- 2016-04-21 MX MX2017013392A patent/MX2017013392A/es unknown
- 2016-04-21 RU RU2017134782A patent/RU2017134782A/ru not_active Application Discontinuation
- 2016-04-21 WO PCT/EP2016/058822 patent/WO2016170018A1/en active Application Filing
- 2016-04-21 JP JP2017554524A patent/JP2018517796A/ja active Pending
- 2016-04-21 SG SG11201708227WA patent/SG11201708227WA/en unknown
- 2016-04-21 CN CN201680022326.1A patent/CN107531825A/zh not_active Withdrawn
- 2016-04-22 TW TW105112702A patent/TW201704272A/zh unknown
- 2016-04-22 AR ARP160101113A patent/AR104351A1/es unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101360769A (zh) * | 2005-03-17 | 2009-02-04 | 陶氏环球技术公司 | 官能化的乙烯/α-烯烃嵌段共聚体组合物 |
CN102143980A (zh) * | 2008-07-03 | 2011-08-03 | 株式会社普利司通 | 用含被保护氨基的酰亚胺化合物官能化的聚合物 |
CN103180352A (zh) * | 2010-09-21 | 2013-06-26 | W.L.戈尔及同仁股份有限公司 | 可膨胀的官能化tfe共聚物细粉末、由其制得的膨胀的官能化制品以及膨胀的制品的反应 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110624204A (zh) * | 2019-08-29 | 2019-12-31 | 青岛三鸿塑料制品有限公司 | 一种防滑性能好的空手道训练垫及其制造工艺 |
CN116396434A (zh) * | 2023-03-13 | 2023-07-07 | 天津大学 | 基于功能化接枝改性提升聚丙烯薄膜高温击穿性能的方法 |
Also Published As
Publication number | Publication date |
---|---|
AR104351A1 (es) | 2017-07-12 |
TW201704272A (zh) | 2017-02-01 |
WO2016170018A1 (en) | 2016-10-27 |
JP2018517796A (ja) | 2018-07-05 |
US20180155480A1 (en) | 2018-06-07 |
KR20170135937A (ko) | 2017-12-08 |
EP3286253A1 (en) | 2018-02-28 |
RU2017134782A (ru) | 2019-04-04 |
US10093762B2 (en) | 2018-10-09 |
MX2017013392A (es) | 2018-01-30 |
SG11201708227WA (en) | 2017-11-29 |
BR112017022100A2 (pt) | 2018-07-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Akiba et al. | Vulcanization and crosslinking in elastomers | |
CN110121514B (zh) | 改性共轭二烯类聚合物和包含其的橡胶组合物 | |
EP1661946A1 (en) | Conjugated diene rubber compositions, process for production of the same and products of crosslinking thereof | |
US9790307B2 (en) | Process for the production of silane-crosslinked polyolefin in the presence of non-tin catalyst and resulting crosslinked polyolefin | |
CN105705564B (zh) | 改性聚合物的方法 | |
CN107531825A (zh) | 改性聚合物的方法 | |
KR20190066564A (ko) | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 | |
CN111630074A (zh) | 改性共轭二烯类聚合物和包含该改性共轭二烯类聚合物的橡胶组合物 | |
CN110121513B (zh) | 改性共轭二烯类聚合物和包含其的橡胶组合物 | |
KR20170076575A (ko) | 고분자 화합물, 이를 이용한 변성 공액디엔계 중합체의 제조방법 및 변성 공액디엔계 중합체 | |
CN107531909A (zh) | 官能化聚合物的方法 | |
Karbalaei‐Bagher et al. | A modus operandi toward interfacial enhancement of ethylene propylene diene monomer rubber/polybenzoxazine blends using EPDM‐grafted‐vinyltrimethoxysilane copolymer | |
JP3583593B2 (ja) | 架橋可能なゴム組成物、及びその架橋ゴム | |
WO2023032663A1 (ja) | ゴム組成物およびタイヤ製品 | |
KR20190066556A (ko) | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 | |
JPH0411501A (ja) | 空気入りタイヤ | |
US11981773B2 (en) | Ring-opened copolymer | |
US20230348702A1 (en) | Compositions which have polyester-polysiloxane copolymers | |
Grigoryeva et al. | Structure-Property Relationships for Reactively Compatibilized Thermoplastic Elastomers from Recycled Polyolefins and Rubbers | |
KR20190066554A (ko) | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 | |
KR20190066560A (ko) | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 | |
JP3155304B2 (ja) | 熱可塑性エラストマー組成物 | |
CN114787232B (zh) | 开环共聚物 | |
JP7188955B2 (ja) | 熱可塑性樹脂組成物とその製造方法 | |
EP4349616A1 (en) | Rubber composition for tires, tread rubber, and tire |
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 | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180102 |
|
WW01 | Invention patent application withdrawn after publication |