CN109294217A - A kind of self-repairing type thermoplastic elastomer and preparation method thereof - Google Patents
A kind of self-repairing type thermoplastic elastomer and preparation method thereof Download PDFInfo
- Publication number
- CN109294217A CN109294217A CN201811078474.2A CN201811078474A CN109294217A CN 109294217 A CN109294217 A CN 109294217A CN 201811078474 A CN201811078474 A CN 201811078474A CN 109294217 A CN109294217 A CN 109294217A
- Authority
- CN
- China
- Prior art keywords
- thermoplastic elastomer
- mass ratio
- added
- self
- tpe
- 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- Withdrawn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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
-
- 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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- 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
- C08J2375/04—Polyurethanes
-
- 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
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Emergency Medicine (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of self-repairing type thermoplastic elastomers and preparation method thereof, belong to the field of engineering technology of thermoplastic elastomer (TPE).The present invention is added the substances such as caprolactam, aminoundecanoic acid and is reacted, form the polyamide-based thermoplastic elastomer (TPE) of mixed type, have preferable shock resistance using polypropylene glycol as soft segment；Poly methylene poly phenyl poly isocyanate is added and carries out chain extension, so that hard section is during stretching, crystallization will not be induced because of stress so that elastomer is hardened, alleviates the damage to elastomer；By substances such as decanedioic acid, citric acids through amidation process, the packing with self-healing performance is obtained, reduces surface tension, increases lubricity, is uniformly dispersed, surface becomes smooth；Physical blowing finally is carried out to elastomer through supercritical carbon dioxide before elastomer molding, abscess is formed, increases the overall performance of thermoplastic elastomer (TPE).The present invention solves the problems, such as that the self-healing properties of current elastomer are poor, bad mechanical property.
Description
Technical field
The invention discloses a kind of self-repairing type thermoplastic elastomers and preparation method thereof, belong to the work of thermoplastic elastomer (TPE)
Journey technical field.
Background technique
Thermoplastic elastomer (TPE) (Thermoplastic elastomer, TPE) is a kind of characteristic with rubber and plastics,
It is known as the material of the function admirable of third generation synthetic rubber, is widely used in the neck such as automobile industry, footwear material, medical treatment and tubing
Domain.In recent years, in order to cope with automobile inside trim and exterior trim, vibration on household appliances or office equipment etc. and
Noise problem, a kind of material-expanded moldings with flexible touch are widely used in multiple fields.Thermoplastic elastic material
It is easy molding and foaming, thus is had been favored by people.At present it is known that the method for preparing thermoplastic elastomer (TPE) is first to prepare heat
Then thermoplastic elastic mixes thermoplastic elastomer (TPE) with foaming agent, the molding modes systems such as injection molding are squeezed out or heated by heating
Standby foamed products, in this way, it is necessary to before continuous extrusion, thermoplastic elastomer (TPE) be uniformly mixed with foaming agent, process
Complexity, used device are more.And the foaming agent that existing foamed material is selected is based on heat decomposition type, such as sodium bicarbonate, azo
Bis-isobutyronitrile etc., expansion rate is fast, and gas release is difficult to control, and the uniformity of foaming is poor, is easy defoaming or aperture, thermoplasticity obtained
Surface of elastomer is coarse, and elastomer bad mechanical property obtained, Boardy Feeling, and hardness is high.Therefore it needs to develop a kind of comprising hair
The novel thermoplastic elastomer composition of infusion does not need in advance during extrusion molding or injection molding by thermoplastic elastic
Body is mixed with foaming agent, can directly obtain foamed products, reduces the production process for preparing foamed products, and pass through foaming heat
It is reasonably combined between thermoplastic elastic component, obtain uniform foam cell, the good foamed products of surface smooth touch.
Summary of the invention
The technical problems to be solved by the invention: for current elastomer self-healing properties it is poor, bad mechanical property ask
Topic provides a kind of self-repairing type thermoplastic elastomer and preparation method thereof.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of self-repairing type thermoplastic elastomer, including thermoplastic elastomer (TPE), the smooth additive of selfreparing；
The thermoplastic elastomer (TPE) are as follows:
(1) according to the mass fraction, 20 ~ 40 parts of caprolactams, 10 ~ 20 parts of aminoundecanoic acids, 3 ~ 7 parts of polypropylene glycols, 8 ~ 10 parts are taken
Hexylene glycol, 20 ~ 30 parts of nylon-11s, 50 ~ 70 parts of distilled water mixing, are passed through nitrogen protection, keep the temperature, be cooled to room temperature, obtain cooling
Object；
(2) it takes poly methylene poly phenyl poly isocyanate 1 ~ 3:8 in mass ratio ~ 10 that dimethylbenzene is added to be stirred, obtains mixed liquor,
205 ~ 215 DEG C are warming up to, mixed liquor 3 ~ 7:2 ~ 5 in mass ratio is taken to be added dropwise in cooled material, controls 30 ~ 50min of time for adding, then
270 ~ 280 DEG C of 30 ~ 40min of heat preservation are warming up to, mixture is obtained, take mixture 10 ~ 20:1 in mass ratio ~ 4 that polytetrahydrofuran is added
Glycol -1000 is cooled to room temperature in 230 ~ 250 DEG C of 2 ~ 4h of heat preservation, is evaporated under reduced pressure to get thermoplastic elastomer (TPE).
The heat-retaining condition of cooled material in the step (1) are as follows: be warming up to 210 ~ 220 DEG C of 60 ~ 90min of heat preservation, then be warming up to
240 ~ 250 DEG C of 1 ~ 4h of heat preservation.
The smooth additive of selfreparing the preparation method comprises the following steps:
S1. take decanedioic acid 1 ~ 3:2 in mass ratio ~ 5:5 ~ 10 that citric acid, diethylenetriamine is added, it is stirred 20 in 25 ~ 30 DEG C ~
30min is passed through nitrogen protection, is warming up to 110 ~ 120 DEG C of 10 ~ 12h of heat preservation, then be warming up to 150 ~ 160 DEG C heat preservation 18 ~ for 24 hours, must stir
Mixture is mixed, takes stirring mixture 8 ~ 10:2 in mass ratio ~ 5 that urea is added, is stirred, is cooled to room temperature in 150 ~ 160 DEG C,
Obtain cooled material a；
S2. it takes cooled material a 2 ~ 5:30 in mass ratio ~ 40 that deionized water is added, adds the emulsifier of cooled material quality 30 ~ 40%
It is stirred, mixture a must be stirred, take stirring mixture 15 ~ 20:3 ~ 8 to be in mass ratio added dropwise in silicone oil, control time for adding
20 ~ 40min filters in 50 ~ 55 DEG C of 2 ~ 5h of heat preservation, takes filtration cakes torrefaction to get the smooth additive of selfreparing.
Emulsifier in the step S2 are as follows: take neopelex 2 ~ 5:4 in mass ratio ~ 7 that Arabic gum is added
Mixing to get.
Silicone oil in the step S2 are as follows: take containing hydrogen silicone oil 2 ~ 5:3 in mass ratio ~ 7 that the mixing of trimethoxy silicone oil is added, i.e.,
?.
A kind of self-repairing type thermoplastic method for producing elastomers, includes the following steps:
It takes thermoplastic elastomer (TPE) 3 ~ 7:2 in mass ratio ~ 5 that the smooth additive mixing of selfreparing is added, adds thermoplastic elastomer (TPE)
The different benzoyl of peroxidating two of mass ratio 5 ~ 10% is kneaded, and then at 140 ~ 150 DEG C, 10MPa 10 ~ 15min of compression molding, cold pressing is obtained
Matrix object takes matrix object to be passed through carbon dioxide, through supercritical carbon dioxide treatment, is cooled to room temperature, and extrusion forming is to get reviewing one's lessons by oneself
Replica thermoplastic elastomer (TPE).
The supercritical carbon dioxide treatment condition are as follows: keep 20 ~ 30min in 60 ~ 90 DEG C, 15MPa.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention is added the substances such as caprolactam, aminoundecanoic acid and is reacted to obtain hard section using polypropylene glycol as soft segment,
And mixed with nylon-11, the polyamide-based thermoplastic elastomer (TPE) of mixed type is formed, wherein the addition of aminoundecanoic acid, is poly-
The backbone molecule of amide copolymer provides segment flexible, so that the flexibility of backbone molecule increases, has broken copolymerization
The regularity of object strand, intermolecular Van der Waals force reduce, and the crystallinity of material reduces, so that the toughness of elastomer obtains
To raising, there is preferable shock resistance；
(2) polymethylene polyphenyl polyisocyanic acid is added on the basis of obtaining polyamide-based thermoplastic elastomer (TPE) in the present invention
Ester carries out chain extension, is connected by newly-generated amido bond with elastomer, finally carries out esterification contracting with polytetrahydrofuran diol -1000
Poly- reaction, obtains thermoplastic elastomer (TPE), the introducing of polytetrahydrofuran diol -1000, so that hard section is during stretching, Bu Huiyin
It induces crystallization so that elastomer is hardened for stress, alleviates the damage to elastomer；
(3) present invention adds urea by substances such as decanedioic acid, citric acids through amidation process, generates and generates hydrogen bond compared with multipotency
Functional group, obtain the packing with self-healing performance, hydrogen bond has high saturability and directionality etc., disconnected by external force in elastomer
When splitting, with periphery, other unpaired hydrogen bonds combine the hydrogen bond energy in upper state, form crosslinking, reduce potential energy, so that
Elastic physical efficiency self-healing, in extrusion process, core material silicone oil can flow to elastomer crosslinked interface, reduce surface tension, increase
Lubricity, so that being uniformly dispersed between elasticity, surface becomes smooth；
(4) present invention finally carries out physical blowing to elastomer through supercritical carbon dioxide before elastomer molding, is formed
The different benzoyl of crosslinking agent peroxidating two is added in abscess, and thermoplastic elastomer (TPE) can absorb great amount of carbon dioxide in the molten state, at
Epipole increases, and forms uniform, the biggish abscess of density, has preferable foam performance, increases the whole of thermoplastic elastomer (TPE)
Body performance.
Specific embodiment
Process for preparation of thermoplastic elastomer are as follows:
(1) according to the mass fraction, 20 ~ 40 parts of caprolactams, 10 ~ 20 parts of aminoundecanoic acids, 3 ~ 7 parts of polypropylene glycols, 8 ~ 10 parts are taken
Hexylene glycol, 20 ~ 30 parts of nylon-11s, the mixing of 50 ~ 70 parts of distilled water, are passed through nitrogen protection, be warming up to 210 ~ 220 DEG C of heat preservations 60 ~
90min, then 240 ~ 250 DEG C of 1 ~ 4h of heat preservation are warming up to, it is cooled to room temperature, obtains cooled material；
(2) it takes poly methylene poly phenyl poly isocyanate 1 ~ 3:8 in mass ratio ~ 10 that dimethylbenzene is added, is stirred 30 ~ 50min,
Mixed liquor is obtained, 205 ~ 215 DEG C is warming up to, mixed liquor 3 ~ 7:2 ~ 5 in mass ratio is taken to be added dropwise in cooled material, controls time for adding 30
~ 50min, then 270 ~ 280 DEG C of 30 ~ 40min of heat preservation are warming up to, mixture is obtained, takes mixture 10 ~ 20:1 in mass ratio ~ 4 to be added poly-
Erythritan -1000 is cooled to room temperature in 230 ~ 250 DEG C of 2 ~ 4h of heat preservation, is evaporated under reduced pressure to get thermoplastic elastomer (TPE).
Emulsifier: take neopelex 2 ~ 5:4 in mass ratio ~ 7 be added Arabic gum mixing to get.
Silicone oil: take containing hydrogen silicone oil 2 ~ 5:3 in mass ratio ~ 7 be added trimethoxy silicone oil mixing to get.
The smooth additive of selfreparing the preparation method comprises the following steps:
S1. take decanedioic acid 1 ~ 3:2 in mass ratio ~ 5:5 ~ 10 that citric acid, diethylenetriamine is added, it is stirred 20 in 25 ~ 30 DEG C ~
30min is passed through nitrogen protection, is warming up to 110 ~ 120 DEG C of 10 ~ 12h of heat preservation, then be warming up to 150 ~ 160 DEG C heat preservation 18 ~ for 24 hours, must stir
Mixture is mixed, takes stirring mixture 8 ~ 10:2 in mass ratio ~ 5 that urea is added, is stirred 1 ~ 3h in 150 ~ 160 DEG C, is cooled to
Room temperature obtains cooled material a；
S2. it takes cooled material a 2 ~ 5:30 in mass ratio ~ 40 that deionized water is added, adds the emulsifier of cooled material quality 30 ~ 40%,
It is warming up to 40 ~ 50 DEG C and is stirred 10 ~ 15h, mixture a must be stirred, stirring mixture 15 ~ 20:3 ~ 8 in mass ratio is taken to be added dropwise to
In silicone oil, 20 ~ 40min of time for adding is controlled, in 50 ~ 55 DEG C of 2 ~ 5h of heat preservation, filters, takes filtration cakes torrefaction smooth to get selfreparing
Additive.
A kind of self-repairing type thermoplastic method for producing elastomers, includes the following steps:
It takes thermoplastic elastomer (TPE) 3 ~ 7:2 in mass ratio ~ 5 that the smooth additive mixing of selfreparing is added, adds thermoplastic elastomer (TPE)
The different benzoyl of peroxidating two of mass ratio 5 ~ 10%, in 90 ~ 100 DEG C, 60rpm/min be kneaded 5 ~ 10min, then at 140 ~ 150 DEG C,
10MPa 10 ~ 15min of compression molding, cold pressing, obtains matrix object, takes matrix object to be passed through carbon dioxide, at supercritical carbon dioxide
Reason keeps 20 ~ 30min in 60 ~ 90 DEG C, 15MPa, is cooled to room temperature, extrusion forming is to get self-repairing type thermoplastic elastomer.
Process for preparation of thermoplastic elastomer are as follows:
(1) according to the mass fraction, 20 parts of caprolactams, 10 parts of aminoundecanoic acids, 3 parts of polypropylene glycols, 8 parts of hexylene glycols, 20 parts are taken
Nylon-11,50 parts of distilled water mixing, are passed through nitrogen protection, are warming up to 210 DEG C of heat preservation 60min, then be warming up to 240 DEG C of heat preservation 1h,
It is cooled to room temperature, obtains cooled material；
(2) it takes poly methylene poly phenyl poly isocyanate 1:8 in mass ratio that dimethylbenzene is added, is stirred 30min, must mix
Liquid is warming up to 205 DEG C, and mixed liquor 3:2 in mass ratio is taken to be added dropwise in cooled material, controls time for adding 30min, then be warming up to
270 DEG C of heat preservation 30min, obtain mixture, take mixture 10:1 in mass ratio that polytetrahydrofuran diol -1000 is added, and protect in 230 DEG C
Warm 2h, is cooled to room temperature, and is evaporated under reduced pressure to get thermoplastic elastomer (TPE).
Emulsifier: take neopelex 2:4 in mass ratio be added Arabic gum mixing to get.
Silicone oil: take containing hydrogen silicone oil 2:3 in mass ratio be added trimethoxy silicone oil mixing to get.
The smooth additive of selfreparing the preparation method comprises the following steps:
S1. it takes decanedioic acid 1:2:5 in mass ratio that citric acid, diethylenetriamine is added, is stirred 20min in 25 DEG C, is passed through nitrogen
Gas shielded is warming up to 110 DEG C of heat preservation 10h, then is warming up to 150 DEG C of heat preservation 18h, obtains stirring mixture, takes stirring mixture by matter
Urea is added than 8:2 in amount, is stirred 1h in 150 DEG C, is cooled to room temperature, obtains cooled material a；
S2. it takes cooled material a 2:30 in mass ratio that deionized water is added, adds the emulsifier of cooled material quality 30%, be warming up to 40
DEG C it is stirred 10h, mixture a must be stirred, taken stirring mixture 15:3 to be in mass ratio added dropwise in silicone oil, control time for adding
20min filters in 50 DEG C of heat preservation 2h, takes filtration cakes torrefaction to get the smooth additive of selfreparing.
A kind of self-repairing type thermoplastic method for producing elastomers, includes the following steps:
It takes thermoplastic elastomer (TPE) 3:2 in mass ratio that the smooth additive mixing of selfreparing is added, adds thermoplastic elastic weight
The different benzoyl of peroxidating two than 5% is kneaded 5min in 90 DEG C, 60rpm/min, then at 140 DEG C, 10MPa compression molding 10min,
Cold pressing, obtains matrix object, matrix object is taken to be passed through carbon dioxide, through supercritical carbon dioxide treatment, keeps in 60 DEG C, 15MPa
20min is cooled to room temperature, and extrusion forming is to get self-repairing type thermoplastic elastomer.
Process for preparation of thermoplastic elastomer are as follows:
(1) according to the mass fraction, 40 parts of caprolactams, 20 parts of aminoundecanoic acids, 7 parts of polypropylene glycols, 10 parts of hexylene glycols, 30 parts are taken
Nylon-11,70 parts of distilled water mixing, are passed through nitrogen protection, are warming up to 220 DEG C of heat preservation 90min, then be warming up to 250 DEG C of heat preservation 4h,
It is cooled to room temperature, obtains cooled material；
(2) it takes poly methylene poly phenyl poly isocyanate 3:10 in mass ratio that dimethylbenzene is added, is stirred 50min, must mix
Liquid is warming up to 215 DEG C, and mixed liquor 7:5 in mass ratio is taken to be added dropwise in cooled material, controls time for adding 50min, then be warming up to
280 DEG C of heat preservation 40min, obtain mixture, take mixture 20:4 in mass ratio that polytetrahydrofuran diol -1000 is added, and protect in 250 DEG C
Warm 4h, is cooled to room temperature, and is evaporated under reduced pressure to get thermoplastic elastomer (TPE).
Emulsifier: take neopelex 5:7 in mass ratio be added Arabic gum mixing to get.
Silicone oil: take containing hydrogen silicone oil 5:7 in mass ratio be added trimethoxy silicone oil mixing to get.
The smooth additive of selfreparing the preparation method comprises the following steps:
S1. it takes decanedioic acid 3:5:10 in mass ratio that citric acid, diethylenetriamine is added, is stirred 30min in 30 DEG C, is passed through nitrogen
Gas shielded is warming up to 120 DEG C of heat preservation 12h, then is warming up to 160 DEG C of heat preservations for 24 hours, obtains stirring mixture, takes stirring mixture by matter
Urea is added than 10:5 in amount, is stirred 3h in 160 DEG C, is cooled to room temperature, obtains cooled material a；
S2. it takes cooled material a 5:40 in mass ratio that deionized water is added, adds the emulsifier of cooled material quality 40%, be warming up to 50
DEG C it is stirred 15h, mixture a must be stirred, taken stirring mixture 20:8 to be in mass ratio added dropwise in silicone oil, control time for adding
40min filters in 55 DEG C of heat preservation 5h, takes filtration cakes torrefaction to get the smooth additive of selfreparing.
A kind of self-repairing type thermoplastic method for producing elastomers, includes the following steps:
It takes thermoplastic elastomer (TPE) 7:5 in mass ratio that the smooth additive mixing of selfreparing is added, adds thermoplastic elastic weight
The different benzoyl of peroxidating two than 10% is kneaded 10min in 100 DEG C, 60rpm/min, then at 150 DEG C, 10MPa compression molding
15min, cold pressing, obtains matrix object, matrix object is taken to be passed through carbon dioxide, through supercritical carbon dioxide treatment, protects in 90 DEG C, 15MPa
30min is held, is cooled to room temperature, extrusion forming is to get self-repairing type thermoplastic elastomer.
Process for preparation of thermoplastic elastomer are as follows:
(1) according to the mass fraction, 30 parts of caprolactams, 15 parts of aminoundecanoic acids, 4 parts of polypropylene glycols, 9 parts of hexylene glycols, 25 parts are taken
Nylon-11,60 parts of distilled water mixing, are passed through nitrogen protection, are warming up to 215 DEG C of heat preservation 80min, then be warming up to 245 DEG C of heat preservation 3h,
It is cooled to room temperature, obtains cooled material；
(2) it takes poly methylene poly phenyl poly isocyanate 2:9 in mass ratio that dimethylbenzene is added, is stirred 40min, must mix
Liquid is warming up to 210 DEG C, and mixed liquor 4:3 in mass ratio is taken to be added dropwise in cooled material, controls time for adding 40min, then be warming up to
275 DEG C of heat preservation 35min, obtain mixture, take mixture 15:2 in mass ratio that polytetrahydrofuran diol -1000 is added, and protect in 240 DEG C
Warm 3h, is cooled to room temperature, and is evaporated under reduced pressure to get thermoplastic elastomer (TPE).
Emulsifier: take neopelex 3:5 in mass ratio be added Arabic gum mixing to get.
Silicone oil: take containing hydrogen silicone oil 3:4 in mass ratio be added trimethoxy silicone oil mixing to get.
The smooth additive of selfreparing the preparation method comprises the following steps:
S1. it takes decanedioic acid 2:3:7 in mass ratio that citric acid, diethylenetriamine is added, is stirred 25min in 27 DEG C, is passed through nitrogen
Gas shielded is warming up to 115 DEG C of heat preservation 11h, then is warming up to 155 DEG C of heat preservation 22h, obtains stirring mixture, takes stirring mixture by matter
Urea is added than 9:4 in amount, is stirred 2h in 155 DEG C, is cooled to room temperature, obtains cooled material a；
S2. it takes cooled material a 3:35 in mass ratio that deionized water is added, adds the emulsifier of cooled material quality 35%, be warming up to 45
DEG C it is stirred 12h, mixture a must be stirred, taken stirring mixture 17:5 to be in mass ratio added dropwise in silicone oil, control time for adding
30min filters in 52 DEG C of heat preservation 3h, takes filtration cakes torrefaction to get the smooth additive of selfreparing.
A kind of self-repairing type thermoplastic method for producing elastomers, includes the following steps:
It takes thermoplastic elastomer (TPE) 4:3 in mass ratio that the smooth additive mixing of selfreparing is added, adds thermoplastic elastic weight
The different benzoyl of peroxidating two than 7% is kneaded 7min in 95 DEG C, 60rpm/min, then at 145 DEG C, 10MPa compression molding 12min,
Cold pressing, obtains matrix object, matrix object is taken to be passed through carbon dioxide, through supercritical carbon dioxide treatment, keeps in 80 DEG C, 15MPa
25min is cooled to room temperature, and extrusion forming is to get self-repairing type thermoplastic elastomer.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking thermoplastic elastomer (TPE).
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking the smooth additive of selfreparing.
Comparative example 3: the thermoplastic elastomer (TPE) of Wuxi City company production.
The self-repairing type thermoplastic elastomer that above-described embodiment is obtained with comparative example is detected, according to ASTMD2240
Hardness, GB/T1039-92 detection of broken tensile strength and elongation at break are detected, ASTMD624 detects tearing strength, obtains
The results are shown in Table 1.
Table 1:
In summary, self-repairing type thermoplastic elastomer effect of the invention is more preferable as can be seen from Table 1, is worth of widely use,
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all within the spirits and principles of the present invention, institute
Any modification, equivalent substitution, improvement and etc. of work should all include again within protection scope of the present invention.
Claims (7)
1. a kind of self-repairing type thermoplastic elastomer, which is characterized in that including thermoplastic elastomer (TPE), the smooth additive of selfreparing；
The thermoplastic elastomer (TPE) are as follows:
(1) according to the mass fraction, 20 ~ 40 parts of caprolactams, 10 ~ 20 parts of aminoundecanoic acids, 3 ~ 7 parts of polypropylene glycols, 8 ~ 10 parts are taken
Hexylene glycol, 20 ~ 30 parts of nylon-11s, 50 ~ 70 parts of distilled water mixing, are passed through nitrogen protection, keep the temperature, be cooled to room temperature, obtain cooling
Object；
(2) it takes poly methylene poly phenyl poly isocyanate 1 ~ 3:8 in mass ratio ~ 10 that dimethylbenzene is added to be stirred, obtains mixed liquor,
205 ~ 215 DEG C are warming up to, mixed liquor 3 ~ 7:2 ~ 5 in mass ratio is taken to be added dropwise in cooled material, controls 30 ~ 50min of time for adding, then
270 ~ 280 DEG C of 30 ~ 40min of heat preservation are warming up to, mixture is obtained, take mixture 10 ~ 20:1 in mass ratio ~ 4 that polytetrahydrofuran is added
Glycol -1000 is cooled to room temperature in 230 ~ 250 DEG C of 2 ~ 4h of heat preservation, is evaporated under reduced pressure to get thermoplastic elastomer (TPE).
2. self-repairing type thermoplastic elastomer according to claim 1, which is characterized in that cooled material in the step (1)
Heat-retaining condition are as follows: be warming up to 210 ~ 220 DEG C of 60 ~ 90min of heat preservation, then be warming up to 240 ~ 250 DEG C of 1 ~ 4h of heat preservation.
3. self-repairing type thermoplastic elastomer according to claim 1, which is characterized in that the smooth additive of selfreparing
The preparation method comprises the following steps:
S1. take decanedioic acid 1 ~ 3:2 in mass ratio ~ 5:5 ~ 10 that citric acid, diethylenetriamine is added, it is stirred 20 in 25 ~ 30 DEG C ~
30min is passed through nitrogen protection, is warming up to 110 ~ 120 DEG C of 10 ~ 12h of heat preservation, then be warming up to 150 ~ 160 DEG C heat preservation 18 ~ for 24 hours, must stir
Mixture is mixed, takes stirring mixture 8 ~ 10:2 in mass ratio ~ 5 that urea is added, is stirred, is cooled to room temperature in 150 ~ 160 DEG C,
Obtain cooled material a；
S2. it takes cooled material a 2 ~ 5:30 in mass ratio ~ 40 that deionized water is added, adds the emulsifier of cooled material quality 30 ~ 40%
It is stirred, mixture a must be stirred, take stirring mixture 15 ~ 20:3 ~ 8 to be in mass ratio added dropwise in silicone oil, control time for adding
20 ~ 40min filters in 50 ~ 55 DEG C of 2 ~ 5h of heat preservation, takes filtration cakes torrefaction to get the smooth additive of selfreparing.
4. self-repairing type thermoplastic elastomer according to claim 3, which is characterized in that the emulsifier in the step S2
Are as follows: take neopelex 2 ~ 5:4 in mass ratio ~ 7 be added Arabic gum mixing to get.
5. self-repairing type thermoplastic elastomer according to claim 3, which is characterized in that the silicone oil in the step S2
Are as follows: take containing hydrogen silicone oil 2 ~ 5:3 in mass ratio ~ 7 be added trimethoxy silicone oil mixing to get.
6. a kind of self-repairing type thermoplastic method for producing elastomers as described in claim 1 ~ 5 any one, feature exist
In the preparation method includes the following steps:
It takes thermoplastic elastomer (TPE) 3 ~ 7:2 in mass ratio ~ 5 that the smooth additive mixing of selfreparing is added, adds thermoplastic elastomer (TPE)
The different benzoyl of peroxidating two of mass ratio 5 ~ 10% is kneaded, and then at 140 ~ 150 DEG C, 10MPa 10 ~ 15min of compression molding, cold pressing is obtained
Matrix object takes matrix object to be passed through carbon dioxide, through supercritical carbon dioxide treatment, is cooled to room temperature, and extrusion forming is to get reviewing one's lessons by oneself
Replica thermoplastic elastomer (TPE).
7. self-repairing type thermoplastic method for producing elastomers according to claim 6, which is characterized in that described overcritical
Carbon dioxide treatment condition are as follows: keep 20 ~ 30min in 60 ~ 90 DEG C, 15MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811078474.2A CN109294217A (en) | 2018-09-17 | 2018-09-17 | A kind of self-repairing type thermoplastic elastomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811078474.2A CN109294217A (en) | 2018-09-17 | 2018-09-17 | A kind of self-repairing type thermoplastic elastomer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109294217A true CN109294217A (en) | 2019-02-01 |
Family
ID=65163194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811078474.2A Withdrawn CN109294217A (en) | 2018-09-17 | 2018-09-17 | A kind of self-repairing type thermoplastic elastomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109294217A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437453A (en) * | 2019-08-14 | 2019-11-12 | 中国科学院兰州化学物理研究所 | A kind of preparation method of low temperature self-healing polymer elastomer |
| CN111471154A (en) * | 2020-05-11 | 2020-07-31 | 中国科学院深圳先进技术研究院 | Light or heat induced self-repairing elastomer and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2098913A1 (en) * | 2008-03-03 | 2009-09-09 | Xerox Corporation | Photoconductive member |
| US20090326087A1 (en) * | 2008-06-27 | 2009-12-31 | Xerox Corporation | Method for treating microcapsules for use in imaging member |
| CN102399357A (en) * | 2011-09-29 | 2012-04-04 | 四川大学 | Preparation method of multi-block nylon polyurethane elastomer |
| CN104327296A (en) * | 2014-11-13 | 2015-02-04 | 四川大学 | Mixed polyurethane foam material and preparation method thereof |
| CN104479127A (en) * | 2014-12-12 | 2015-04-01 | 东华大学 | Caprolactam hydrolytic polymer and hydrolytic polymerization method thereof |
| CN105440692A (en) * | 2015-12-14 | 2016-03-30 | 华南理工大学 | Microcapsule-type self-repairing polysiloxane elastomer and preparation method thereof |
-
2018
- 2018-09-17 CN CN201811078474.2A patent/CN109294217A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2098913A1 (en) * | 2008-03-03 | 2009-09-09 | Xerox Corporation | Photoconductive member |
| US20090326087A1 (en) * | 2008-06-27 | 2009-12-31 | Xerox Corporation | Method for treating microcapsules for use in imaging member |
| CN102399357A (en) * | 2011-09-29 | 2012-04-04 | 四川大学 | Preparation method of multi-block nylon polyurethane elastomer |
| CN104327296A (en) * | 2014-11-13 | 2015-02-04 | 四川大学 | Mixed polyurethane foam material and preparation method thereof |
| CN104479127A (en) * | 2014-12-12 | 2015-04-01 | 东华大学 | Caprolactam hydrolytic polymer and hydrolytic polymerization method thereof |
| CN105440692A (en) * | 2015-12-14 | 2016-03-30 | 华南理工大学 | Microcapsule-type self-repairing polysiloxane elastomer and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LING LIU等: "A Novel and Non-Cytotoxic Self-Healing Supramolecular Elastomer Synthesized with Small Molecular Biological Acids", 《MACROMOLECULAR》 * |
| 易春旺: "PA6-MDI-PA6/PTMG热塑性弹性体的制备与性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 杨保平等: "甲基硅油微胶囊/聚苯乙烯复合材料及其摩擦学性能", 《高分子材料科学与工程》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437453A (en) * | 2019-08-14 | 2019-11-12 | 中国科学院兰州化学物理研究所 | A kind of preparation method of low temperature self-healing polymer elastomer |
| CN110437453B (en) * | 2019-08-14 | 2021-09-21 | 中国科学院兰州化学物理研究所 | Preparation method of low-temperature self-healing polymer elastomer |
| CN111471154A (en) * | 2020-05-11 | 2020-07-31 | 中国科学院深圳先进技术研究院 | Light or heat induced self-repairing elastomer and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100467533C (en) | Thermoplastic elastomer composition and formed article | |
| CN104877335B (en) | A kind of thermoplastic polyurethane elastomer expanded bead and preparation method thereof | |
| CN109440484A (en) | A kind of soft solvent-free flame-retardant type polyurethane synthetic leather and preparation method thereof | |
| CN104327266B (en) | Preparation method of polyamide 6 thermoplastic elastomer resin | |
| CN109294217A (en) | A kind of self-repairing type thermoplastic elastomer and preparation method thereof | |
| CN103409101B (en) | Polybutadiene rubber modified waterborne polyurethane adhesive and preparation method thereof | |
| CN106085325B (en) | The epoxy adhesive of tertiary-amine modified liquid nitrile rubber toughening | |
| CN110724375A (en) | TPU/EVA supercritical foaming composite material and preparation method thereof | |
| CN105294991A (en) | Cold cure high resilient foam and preparation method | |
| CN101805486A (en) | Thermoplastic rubber sponge | |
| CN107739589A (en) | Low melting point thermoplastic polyurethane adhesive and preparation method thereof | |
| CN102775537A (en) | High-strength PVC (polyvinyl chloride) paste resin and production method thereof | |
| CN106220809A (en) | A kind of high fire-retardance graphite coating polyurethane and preparation method thereof and construction method | |
| CN106220922A (en) | Dynamic vulcanization polypropylene flame redardant/nitrile rubber thermoplastic elastomer and preparation method thereof | |
| CN110591250B (en) | PVC (polyvinyl chloride) foam material for sports shock pad and preparation process thereof | |
| CN114196136B (en) | PVC yoga mat and preparation method thereof | |
| CN106883591B (en) | Method for utilizing polyurethane waste material and elastomer | |
| US2424883A (en) | Paraformaldehyde modified reaction products of diisocyanates with linear polyester polyamide | |
| CN111234492A (en) | PLA/TPU supercritical foaming composite material and preparation method thereof | |
| CN106866928A (en) | Polyurethane high intensity hydrophily sponge and preparation method thereof | |
| US2281415A (en) | Polyester amides | |
| CN111285991A (en) | Polyurethane mouth mask cotton polyester soft sponge and preparation method thereof | |
| CN117069905A (en) | Slow rebound bio-based sponge and preparation method and application thereof | |
| CN108192073A (en) | Padded coaming that a kind of wide temperature range domain uses and its preparation method and application | |
| JP2534378B2 (en) | Stretchable non-woven fabric |
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: 20190201 |
|
| WW01 | Invention patent application withdrawn after publication |