CN107057005A - A kind of block copolymer of fragrant alkene, conjugated diene and epoxides and preparation method thereof - Google Patents
A kind of block copolymer of fragrant alkene, conjugated diene and epoxides and preparation method thereof Download PDFInfo
- Publication number
- CN107057005A CN107057005A CN201710200610.XA CN201710200610A CN107057005A CN 107057005 A CN107057005 A CN 107057005A CN 201710200610 A CN201710200610 A CN 201710200610A CN 107057005 A CN107057005 A CN 107057005A
- Authority
- CN
- China
- Prior art keywords
- block
- block copolymer
- epoxides
- section
- conjugated diene
- 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.)
- Pending
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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
- A61K9/7023—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms
- A61K9/703—Transdermal patches and similar drug-containing composite devices, e.g. cataplasms characterised by shape or structure; Details concerning release liner or backing; Refillable patches; User-activated patches
- A61K9/7038—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer
- A61K9/7046—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds
- A61K9/7069—Transdermal patches of the drug-in-adhesive type, i.e. comprising drug in the skin-adhesive layer the adhesive comprising macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. polysiloxane, polyesters, polyurethane, polyethylene oxide
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2648—Alkali metals or compounds thereof
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Pharmacology & Pharmacy (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Dermatology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to block copolymer of a kind of fragrant alkene, conjugated diene and epoxides and preparation method thereof, the block copolymer constitutes 3 to 13 blocks by the homopolymer and/or copolymer of monomer, the sequence of backbone block is adjacent with block of different nature, by the parameter regulation such as the composition of each block, molecular weight and molecualr weight distribution, microstructure, block sequence and quantity, function end group, block copolymer is set to have the thermoplastic elastomer (TPE) attribute characteristic compatible with polarity compound concurrently.What preparation method was carried out in two continuously connected technical process, its production process efficiency high, material consumption be low and nontoxic pollution-free, and product meets " greenization " environmental protection and power conservation requirement.The block copolymer is that a new generation is used as traditional Chinese medical science patch agent melt pressure sensitive macromolecule versatile building blocks, with low dosing temperature, big drugloading rate, the good characteristic that PHYSIOLOGICALLY COMPATIBLE is good and peeling force is controllable.
Description
Technical field
The invention belongs to the material modified field of high-molecular block copolymer.More particularly to it is applied to through the percutaneous drug delivery traditional Chinese medical science
A kind of fragrant alkene of the hot-fusible pressure-sensitive adhesive of patch agent pharmaceutical carrier base material, the block copolymer of conjugated diene and epoxides and
Its preparation method.
Technical background
The mankind, which cure the disease into medicine, three kinds of methods, i.e., orally, have an injection and percutaneous dosing.The progress of modern age medicine and pharmacology, latter
Mode has significant advantage and paid high attention to, and last decade obtains high speed development in developed country.
China's percutaneous dosing has thousands of years history, and the traditional Chinese medical science medical ointment plaster patent medicine successfully used is countless, is one huge
Treasure-house.But Topical paste patch auxiliary material is that pharmaceutical carrier base material is not resolved for a long time.Using natural rubber gasoline solution as
Traditional Chinese medicine ointment patch base material occupies leading position, and such patch agent has the serious problems of skin infection allergy when using, production
Process is again very dangerous and pollutes environment.Alternative materials are found to be proposed out.
Last century the nineties, send out with the styrene block copolymer market application technology of external large-scale industrial production
Exhibition, occurs in that environmentally friendly third generation jointing material, i.e. hot-melt pressure sensitive adhesive (abbreviation HMPSA).With styrene-isoprene-benzene
Ethene (abbreviation SIS) is the hot-fusible pressure-sensitive adhesive of main body, (sanltary towel, Er Tonghe on life, office, packaging and medical products
Adult diaper, sanitary mattress and medical adhesive tape etc.) widely used, and obtain the accreditation of beautiful FDA and European Union's relevant criterion.
In view of SIS is promoted applied to Traditional Chinese medicine ointment patch in the HMPSA excellent properties showed and country's SIS industrial productions
Research and development, last decade occurs in that some patents successively.Chinese patent CN102093831A, is proposed using 35-70%SIS as main material,
With the combination of general tackifying resin, plasticising oil and age resistor, HMPSA is made in a point two step hot melts, then active Chinese medicine is added into heat
In molten shape HMPSA, on even spread to back lining materials, turn into patch agent finished product after cooling.Chinese patent CN101899276A,
In typical SIS HMPSA, polarity compound acrylate and polyethylene glycol component are introduced, the HMPSA being made both is kept lipophilic
Property again have hydrophily, i.e., with amphiphilic.Its preparation method is completed in two steps, and the first step is 170-180 DEG C in banbury
Under, make SIS, acrylate and compatilizer banburying uniform；Second step in stirred tank at 150 DEG C, by above-mentioned material and plasticising
Oil, tackifying resin hot melt physical mixed, are made for be adapted to the amphiphilic basic material of percutaneous dosing Traditional Chinese medicine ointment patch.It is Chinese special
Sharp CN103849100A, it is proposed that a kind of for plaster and the SIS of patch, specifies the ratio of three sections of things and two sections of things in its SIS
Scope, two kinds of block things each styrene, isoprene ratio and molecular weight ranges.By itself and general purpose tie resins, plasticising oil
With age resistor combination, the carrier HMPSA of high drug load, low dosing temperature and the low traditional Chinese medicine plaster of peeling force and patch is prepared for.
Chinese patent CN104449488A, discloses a kind of grafting property polystyrene thermoplastic elastomer base hot-fusible pressure-sensitive adhesive and preparation side
Method.Its design is on SIS graft SIS-g-PB or SIS-g-PI strand, with epoxide group and alkadienes branch
Chain is randomly distributed in the isoprene block of SIS main chains, and epoxide group provides hydrophilic drugs release channel, and alkadienes side chain is responsible for
Adjust the adhesion property of hot-fusible pressure-sensitive adhesive system, it is possible to reduce epoxide group influences on system adhesiveness.The patent overcomes
The physical method of additional hydrophilic component causes the disadvantage that HMPSA adhesivenesses decline in SIS.Also mitigate the isoprene in SIS
The chemical method of polar group is introduced directly on block molecule chain, makes HMPSA compatibilities and the impaired degree of adhesiveness.
The content of the invention
It is an object of the invention to overcome the shortcomings of that prior art is present and defect, exploitation is a kind of to be had to medical external medicament
The polymer carrier of extensive compatibility, is particularly suitable for through percutaneous drug delivery traditional Chinese medical science patch agent pharmaceutical carrier basic material
A kind of block copolymer of fragrant alkene, conjugated diene and epoxides and preparation method thereof.
The block copolymer of a kind of fragrant alkene, conjugated diene and epoxides that the present invention is provided, it is characterised in that adopt
The many block sequences being connected with heterogeneity monomer-polymer main chain are arranged, and make polyisoprene blocks molecular structure constant,
So as to maintain SIS superior compatibilities and adhesive capacity.The block copolymer includes fragrant alkene, conjugated diene and epoxidation
The homopolymer and/or copolymer of the class monomer of thing three, wherein block copolymer block number are 3 to 13 blocks, preferably 4 to 9
Block；The sequence of each block of backbone is adjacent by block of different nature.Pass through each block polymer and/or copolymer
Composition, molecular weight and molecualr weight distribution, alkadienes microstructure, each block polymer property, block sequence and quantity, function end
Multiple macromolecular parameter regulations such as base, make that block copolymer integrally has thermal plastic elastomer's attribute concurrently and same polarity compound is compatible
Characteristic.Meet the different application requirement as hot-fusible pressure-sensitive adhesive (HMPAS) and rubber plastic modified material.
Fragrant alkene, is, there is provided network physical " crosslinking points ", to be as " plastics " hard block described in block copolymer of the present invention
HMPAS contributes intensity and hardness.Fragrant alkene include styrene, methyl styrene, divinylbenzene, talan or/and they
Mixture.Polyarylene hydrocarbon is based on styrene, a small amount of rear three kinds of homologues to be suitably added, to improve certain property of the block
Matter, such as glass transition temperature and the degree of branching.
Conjugated diene described in block copolymer, is butadiene, isoprene or/and their mixtures.Polydiene
Block, by the hard phase domain grappling of fragrant alkene during normal temperature, for thermoplastic elastomer (TPE) provide high resiliency and with other compound phase capacitives.It is poly-
Isoprene has very prominent high resiliency and compatibility, SIS is turned into HMPSA main components.But to improve modulus or low temperature properties,
Add some butadiene or introduce polybutadiene block.Conjugated diene is used with, can make isoprene degradation with aging and fourth two
Alkene aging interlinkage balance, improves HMPSA resistances to ag(e)ing.In the present invention, also change HMPSA using alkadienes microstructure
3,4 structures, which can be improved, in matter, such as increasing polyisoprene blocks grasps adhesiveness.
The epoxides, refers to oxirane, expoxy propane, epoxy butane or/and their mixtures, and epoxy chlorine
Propane and epoxidized soybean oil etc..Line style or branching type polyethers that they are formed, backbone structure unit contain the oxygen key of carbon one, make this embedding
Section thing has polarity, and hydrophily or same polarity compound consistency property are provided to block copolymer.According to application requirement, adjustment
Lipophilic and hydrophilic sex ratio, to select epoxides to account for the 5-50% scopes of block copolymer total amount.
The present invention provides a kind of preparation method of the block copolymer of fragrant alkene, conjugated diene and epoxides, is to adopt
With specific organolithium anionic polymerization, completed in two manufacturing process being continuously connected.
1. in the tank reactor (see Fig. 1) by 1 to 3 series winding, by different product requirement, determine and add respectively in each kettle
Enter different solvents, monomer, butyl lithium, the quantity of activator, composition and order, anionic polymerization is carried out in kettle.With
Material adds flow velocity, residence time and relevant temperature, the monomer of each block polymerization is converted completely, to ensure copolymerization physical property
The stabilization of matter and repetition.Each reactor has interior cold and chuck to carry out temperature control auxiliary operation.It is different using being put into each kettle
The successive reaction mode of raw material, the big steady quality of production capacity batch interval can also be prepared in a kettle, but production efficiency
Low and power consumption is high.Block is differed, and reaction temperature is different, but polymerization temperature should be controlled in 40-120 DEG C of scope；Pressure value should height
In monomer reaction temperature correspondence balance pressure (0.2-0.8Mpa) used in block.The intermediate products prepared by above-mentioned reactions steps
It is introduced into surge tank (4) and carries out temperature adjustment and homogenizing.
2. the intermediate through processing in surge tank (4), adds passivator and is polymerize below instead with slowing down and controlling herein
The speed answered.Hereafter with being quantitatively pumped into extrusion reaction unit (5).Twin-screw extrusion reacts unit 5, by transportation section (5-1), instead
Section (5-2), decompression section (5-3) are answered, section (5-4), preceding devolatilization section (5-5), rear devolatilization section (5-6), boost section (6) is terminated and gets to know
Pelletizing section (7) composition.Reaction mass is after transportation section (5-1), into the 1-3 conversion zone of (5-2), every section of addition varying number
The epoxides or monomer different with composition, the temperature control of conversion zone is in 60-140 DEG C of scope, and the monomer such as epoxides is added
Gross weight, it is different by block copolymer Property requirements, it is the 5%-50% of copolymer.After each conversion zone, if a decompression
Section (5-3), a part of solvent and light component are flashed herein, quickly take away heat.Reactant, which enters, after flash distillation terminates section (5-4),
Age resistor (phenols or hindered phenol compound) (7) is added herein, prevents the degraded and friendship of the lower segmented copolymer of hot oxygen effect
Chain.Material enters preceding devolatilization section (5-5) afterwards, sloughs big portion's solvent under normal pressure and low pressure, material continue heating heat into
Enter rear devolatilization section (5-6) and remove a small amount of residual monomer under vacuo, the devolatilization section after several series windings, block copolymer progressively rises
Temperature is from 120 DEG C to 180 DEG C, and fugitive constituent in block copolymer is down to 0.1%-0.02% by vacuum from 80Kpa to 10Kpa.Wherein
Residual styrene content answers ＜ 0.04%, to meet using the demand to smell.The volatile matters such as the solvent of removing, by cryogenic condensation
Into liquid, recovery purifying separation Posterior circle is used.
Above-mentioned product is pressurized (6), into expressed water incision of getting to know after devolatilization section completes melting devolatilization processing through gear pump
Grain system (8), block copolymer cooling is dehydrated through centrifugal dehydrator (9) in spherical particle glue slurry, enters vibratory sieve and delivered to by wind
Feed bin (10), weighed packed storage.
The twin-screw extrusion reaction unit (5), according to product property and the trade mark, can adjust the length in Ge Duan areas (with spiral shell
Shank diameter multiple is represented).Unit total slenderness ratio is optimized for 48-80 in 48-100 scopes.And screw diameter according to product yield in φ
The scopes of 25- φ 150, generally in φ 35- φ 100.
Saturation hydrocarbon flux of the present invention described in preparation method is the alkane of 4-6 carbon numbers, they be butane, pentane, oneself
Alkane and their own isomer or their mixtures.Solvent composition, which is mainly, to be met weather conditions, energy-conservation and is engineered
Composite demand.Preferably hexamethylene and n-hexane 8-9/2-1 scalemic thereofs.
Described passivator is lewis acid compounds and makes anion living chain increasing option and occur part chain turn
The material of shifting, such as carbon dioxide, minor amount of water, dibutyl magnesium, alkyl aluminum, methyl styrene and toluene or/and mixing between them
Compound.Polymer ends lithium alkylide active ion pair, there is certain balance in it, between free ion when introducing lewis acids
Compound, balance tends to Tight ion pair, its degree of ionization is deteriorated, and chain growth speed slows down.Alkaline-earth metal organic matter is such as
The introducing of magnesium, reaction speed reduces an order of magnitude.Although action principle can be explained in theory, because process is complicated,
Particularly complex effect etc. can not still understand explanation.We are according to experimental result, and the total addition of passivator is butyl lithium quality 2-
100 times, preferably 10-80 times.
The twin-screw extrusion reaction unit (5) used described in the preparation method of the present invention, assume responsibility for post-polymerization, solvent
Reclaim and the removing of a small amount of residual monomer is until the whole production tasks of product post-processing molding, granulating.Needed for reply, the swivel nut of unit 5
And respective threaded rod, 8 functional section areas are constituted in order：(5-1) conversion zone area of transportation section area (5-2) and vacuum flashing section area (5-
3), conversion zone area and vacuum flashing section area, 1 to 3 is set to according to epoxides and amount of monomer.After reaction terminates,
Material is terminating section area addition age resistor, is general phenol and Hinered phenols, such as 1101,1076.Add the finished product of age resistor
Solution takes heating and decompression means, makes product desolvation respectively in preceding devolatilization section area (5-5) and rear devolatilization section area (5-6)
And residual monomer, finally to die head pelletizing section area (8).Unit draw ratio 48-100, has certain change with product grade difference.Its
Diameter is chosen with production capacity difference in φ 25 to φ 150.
The characteristics of block copolymer of the present invention is as HMPSA：During applied to carrying medicine base material through the agent of percutaneous drug delivery traditional Chinese medical science patch,
With relatively low fusing point, be conducive to the protection and medicine blending of Chinese medicine property and be coated with；Block copolymer maintains SIS attributes tool
The lipophilicity having had, and have the compatibility to polar compound concurrently, then reflect the adaptability to aqueous pharmaceutical, and have when using
There is absorption of perspiration.
The preparation method of the present invention is completed in two technical process being continuously connected, and absorbs " extrusion reaction " advanced skill
Art, its production efficiency is high, material consumption is low, monomer is converted entirely, process no waste discharge, meets " greenization " environmental protection and power conservation requirement.
The block copolymer product is that a new generation is used as traditional Chinese medical science patch agent melt pressure sensitive macromolecule versatile building blocks, with low dosing temperature
Degree, big drugloading rate, the good characteristic that PHYSIOLOGICALLY COMPATIBLE is good and peeling force is controllable.Above-mentioned block copolymer preparation method characteristic has aobvious
The superiority of work.In a continuous closed system, different material is added by each phase sequence and changes process conditions, with regard to energy
Complete all round process of complicated segmented copolymer.Method is efficient, monomer conversion is complete, contamination-free is excluded, and meets green
Change and require.
Block copolymer of the present invention can be used as base material and rubber plastic modified material through percutaneous drug delivery patch agent as HMPSA.
Brief description of the drawings
Fig. 1 block copolymer preparation technology flow charts
Embodiment
The present invention is further described with the following example by the present invention, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
In 10 liter reactor systems of two series connection, first replaced with the heating of reacting kettle jacketing thermal medium and High Purity Nitrogen,
Oxygen, water content is reached 3PPM, then 100 grams of 4000 grams of hexamethylene and styrene are added to first reactor, opening stirring makes kettle
Temperature reaches 60-70 DEG C, adds butyl lithium 17mmol, carries out living anion polymerization reaction, sequentially adds isoamyl two every 60 points later
350 grams of alkene, 100 grams of styrene, 350 grams of isoprene, 100 grams of styrene, five step courses of reaction control maximum temperature are no more than
100 DEG C, finally stop 60 points and terminate reaction.
The whole is transferred in second reactor, stirring temperature adjustment is opened to 50-60 DEG C, the toluene for adding alkyl aluminum is molten
58 grams of liquid, declines system reactivity, and chain growth speed slows down.Reaction mass is transferred to screw diameter for φ 25, twin-screw
In the feeder of extrusion reaction unit.This unit swivel nut and screw element composition are as follows：Transportation section 4D (25 be a D), reaction
Section plus-minus pressure section 10D totally two, terminates section 4D, preceding devolatilization section 8D two, rear devolatilization mouthful section 8D two, extruding zone 4D.Adjustment turns
Speed is at 120-200 revs/min, and segmented copolymer solution is controlled in 2000g/h flow velocitys, is continuously added to twin-screw extrusion reaction machine
(5) in, oxirane and expoxy propane (9: 1) 100g/h are added altogether in first and second conversion zone, conversion zone temperature control is 120
Below DEG C, reactant adds antioxidant 1010 solution (10%) addition 20g/h in termination section, and preceding devolatilization mouthful material is heated to
120 DEG C, rear to enter decompression section devolatilization at ambient pressure, later three devolatilizations mouthful depressurize bar successively in 80kpa, 40kpa, 10kpa
Devolatilization under part, temperature and pressure cooperation, in 120-160 DEG C of scope, make final reach of product volatilization be less than 0.1% level.Extract out molten
Agent is reclaimed to purify after separating heavy and used again by compression condensation.In extrusion pelletizing section, product is by the air-cooled pelletizing of nitrogen.Yield
500g/h, product block copolymer (numbering SANGER-1) is 6 block copolymers, styrene-content 24wt%, product fusing point model
Enclose 40 DEG C -94 DEG C, relative hydropathic coefficient 29.5%.
Embodiment 2
On the identical experiment device of embodiment 1, add (9/1) 4200 gram of hexamethylene and hexanes mixtures to the first reactor,
100 grams of styrene, kettle is warming up to 60 DEG C, opens after stirring, plus 0.019mmol butyl lithiums, 60 points, sequentially adds 350 grams of isoamyls two
Alkene, 60 grams of styrene, 350 grams of isoprene, 100 grams of styrene, 350 grams of isoprene, styrene and divinylbenzene mixing
60 grams of thing (wherein containing divinylbenzene 5 grams).Each section of reaction time：Plus 60 points are reacted after styrene, plus reacted after isoprene
40 points.Reaction enters the second reactor after terminating, and temperature adjustment is to 60 DEG C under agitation, and adds after 43 grams of dibutyl magnesium toluene solution,
It is transferred in twin-screw extrusion reaction machine feeder, with 2800g/h speed continuous φ 25, the L/D=64 used into embodiment 1
Twin-screw extrusion reaction unit (5) add reaction mass.Oxirane is added altogether in first and second conversion zone and epoxy butane is common
86g/h (8.5: 1.5), reaction temperature is controlled below 100 DEG C, is terminated section and is added antioxidant 1076 and 168 (1: 2) solution
(10%) 80g/h.Other devolatilization condition be the same as Examples 1.Product (numbering SANGER-2) 780g/h, is 8 block copolymers, benzene second
Alkene content 20.7wt%, 40 DEG C -78 DEG C of product melting range, relative hydropathic coefficient 15.2%.
Embodiment 3
3 polymeric kettle sealing systems of one 20 liters of series connection, every kettle has chuck and interior cold auxiliary temperature control, system water, oxygen
Residual volume is less than 5ppm, and the first reactor maintains 80 DEG C, starts stirring, successive reaction mode production is carried out, from bottom with 9000
Gram/h speed adds solvent hexamethylene and 1500 grams/h 20wt% styrene solutions, adds butyl lithium solution 48.6mmol/h.
4500 grams/h isoprene solutions containing 33.3wt%, 30 points of backward second reactor bottoms are added after 40 points in the middle part of a reactor
Added again in the middle part of two kettles with 4500 grams/h isoamyls containing 33.3wt% after adding the solution 1000g/h containing styrene 20%, 30 points
Diene solution, 30 points of backward 3rd bottom portions add the solution of 20wt% containing styrene 1500g/h, and 40 points in the middle part of three kettles plus containing different
Pentadiene 33.3wt% solution 1000g/h, from the 3rd reactor top discharge reactant to accumulator still (50 liters).Herein through 3.3
Hour collects reaction solution 23kg altogether, and the system of continuous polymerization has now been established in 3 kettle systems, continues to grasp with above-mentioned state
Make, production throughput is 4.13kg per hour.Production capacity is 3 times (during yield/liters) of embodiment 1.By material in accumulator still
Temperature is adjusted to 60 DEG C, and adds alkyl aluminum toluene solution 240g/h.After mixing half an hour twin-screw extrusion reaction is sent to from top
Stored in the feeder of unit.Above-mentioned segmented copolymer solution constant displacement pump is sent to experiment 1 with 2500kg/h speed herein
φ 25, L/D=64 twin-screw extrusions react the extruding zone of unit, and oxirane and epoxy fourth are added altogether in two conversion zones
Not more than 120 DEG C of alkane mix monomer 150g/h (ratio 9: 13) temperature.Age resistor 1010 (10wt%) is added terminating section
Solution 30g/h, other condition be the same as Examples 1.Obtain product 600g/h (numbering is SANGER-3), the block copolymer of line style 7, benzene second
Alkene content 14.5wt%, 37 DEG C -75 DEG C of product melting range, relative hydropathic coefficient 38.8%.
Using comparing embodiment 4
Seven kinds of common SIS (product grade 1161,1105,1126.SN-810, SN-815, SN-811, SN- are bought into market
818) verify and compare with embodiment product progressive：
By being contrasted with three kinds of trade mark properties of commercially available seven kinds of trades mark and the embodiment of the present invention, it may be said that bright segmented copolymer
The characteristics of as HMPSA：With 100 DEG C of fusing points of ＜, Traditional chinese medicine medicament quality is protected, and be conducive to medicine to blend and be coated with；
And hydrophilic coefficient reflection to the compatibility of polar compound and when using absorption of perspiration.
Application Example 5
Using the segmented copolymer of the present invention for framework material and commercially available general purpose tie resins, plastify oil, antioxidant etc. and mix
The HMPSA application features for being blended standby percutaneous dosing are as follows：
1. with (SANGER-2) ointment plaster formula and property in the segmented copolymer of the preparation of embodiment 2：
Embodiment 2, SANGER-28 block copolymers, styrene-content 20.7wt%, 42 DEG C of -83 DEG C of (incipient meltings of melting range
42 DEG C of point, 83 DEG C of fine melt point), relative hydropathic coefficient 15.2%.
Formula：
Preparation method：
Stirred tank is warming up to 180 DEG C under protection of ammonia, first makes SANGER-2, SIS, plasticizing oil and antioxidant mixing molten
Change, being down to 140 DEG C, to add tackifying resins fusing uniform, then be down to 100 DEG C and add after Chinese medicine nostrums stir evenly, i.e., heat be applied to cloth cover into
Topical paste patch piece finished product.Directly spread on related parts of human body.
Property：
Before dosing, initial bonding strength 24#Ball, peel strength 14.5N/25mm (phenolic aldehyde piece), holds sticky ＞ 48 hours.After dosing,
Drugloading rate rheumatalgia-relieving plaster patent medicine 20%, patch medicine glue thickness 0.2mm, spreads on the back of the body, arm, evaluates：It is nonirritant, no allergy.Skin
Paste comfortable, adhesiveness is moderate.It is easy to peel off, and does not remain.Drug effect makees the suitable of base material with commercialization natural rubber.Sweat proof is excellent
It is good, do not fall off.
2. segmented copolymer drug paste formula and property are prepared with embodiment 3 (SANGER-3)：
Styrene-content 14.5wt%, 37 DEG C -76 DEG C of melting range, relative hydropathic coefficient 38.8%.
Formula：
Preparation method：
Be the same as Example 5 1., first by segmented copolymer, plasticizing oil, SIS antioxidant 180 DEG C fusing stir well it is even, cooling
To 140 DEG C plus two kinds of tackifying resins.100 DEG C of adding medicines are down to again, and heat is applied to cloth cover into patch agent piece.
Property：
Before dosing：Tack 32#, peel strength 5.14N/25mm hold viscous by (30 points × 300g, displacement ＜ 3mm).Separately
Add after strychnia, (the μ g/cm of transdermal penetration rates 4.432× h), accumulate within 24 hours transdermal (the μ g/cm of amount 29.22).Add life
Alkaloids, polyalcohol and polyphenol extract combination drug complete miscibility.Paster is transparent, and tack is good.Human body skin is sticked 12 hours
More than, it is non-stimulated.Peeling force is good, and skin is not remained.
Claims (5)
1. a kind of block copolymer of fragrant alkene, conjugated diene and epoxides, it is characterised in that the block copolymer bag
Include the homopolymer or/and copolymer of fragrant alkene, conjugated diene and the class monomer of epoxides three, wherein, block copolymer it is embedding
Hop count is 3 to 13 blocks, and each block sequence of backbone is adjacent by block of different nature, passes through the homopolymerization of each block
The composition of thing and/or copolymer, molecular weight and molecualr weight distribution, alkadienes microstructure, each block polymer property, block sequence
Row and quantity, multiple macromolecular parameter regulations of function end group, make block copolymerization have thermoplastic elastomer (TPE) attribute and polarity concurrently
The compatible characteristic of thing；
The fragrant alkene is styrene, methyl styrene, divinylbenzene, talan, ethylbenzene ethene or their mixture；
The conjugated diene is butadiene, isoprene or their mixtures；
The epoxides is oxirane, expoxy propane, epoxy butane or their mixtures, epoxychloropropane or epoxy soybean
Oil, the total addition of epoxides is the 5-50wt% of block copolymer.
2. the block copolymer of fragrant alkene according to claim 1, conjugated diene and epoxides, it is characterised in that described embedding
The block number of section copolymer is 4 to 9 blocks.
3. the preparation method of the block copolymer of a kind of fragrant alkene of claim 1, conjugated diene and epoxides, is included in
The following steps carried out in the technical process that two continuously connect：
(1), it is made up of under High Purity Nitrogen protection 1 to 3 series connection tank reactor in sealing system, it is big by block copolymer backbone
The sequence different with adjacent blocks property of the block number of molecule, according to different block copolymer properties, determines what each segmentation was added
Fragrant alkene, conjugated diene and epoxide monomer species, weight and corresponding butyl lithium, activation dosage, to first kettle (1) or/and
(2,3) each kettle batch is continuously added to saturated hydrocarbon solvent, monomer, butyl lithium, activator, carries out anionic polymerization, polymerization
Temperature is 40 DEG C -120 DEG C, and pressure is correspondence saturated vapor pressure, and residence time and reaction temperature enable the monomer of each block polymerization
Enough conversions completely；
(2) intermediate product made from step 1, is sent into surge tank (4) to carry out after temperature adjustment and homogenizing, passivator is added, then use pump
Extraction be sent to twin-screw extrusion reaction unit (5) transportation section (5-1), after by conversion zone (5-2) 1-3 conversion zone, often
Section adds not same amount epoxides or monomer, and epoxides total amount is the 5%~50% of block copolymer, conversion zone Stress control
In 1.0-2.0MPa, temperature is 60-140 DEG C；A depressor area (5-3) is set after each conversion zone (5-2), in this partial reaction thing quilt
Flash distillation；Reacted section of material is laggard to terminate section (5-4), adds age resistor (7)；Subsequently into preceding devolatilization section (5-5), under low pressure
Desolvation and a small amount of residual monomer；This is after in rear devolatilization section (5-6), in 120-180 DEG C of negative pressure 80KPa-10KPa and temperature
Volatile matter in product is down to 0.1%-0.02%, and the non-product composition of reaction system is condensed into liquids recovery, after purification
Recycle；
(3), the product handled through devolatilization, is pressurized with gear pump (6) into melt flow stream, underwater pellet cutting system (8) is squeezed into through die head,
Product is starched in spherical particle glue, is dehydrated (9) through supercentrifuge, wind delivers to feed bin (10) packaging and storage；
The saturated hydrocarbon solvent is carbon number 4-6 alkane；
The activator is ether or amine polar compound；
The passivator is lewis acid compounds, minor amount of water, carbon dioxide, toluene, alkyl aluminum, dibutyl magnesium, methylbenzene second
Alkene or and their mixtures, addition is calculated as 10-100 times with butyl lithium mass number.
4. preparation method according to claim 3, it is characterised in that the saturated hydrocarbon solvent is butane, pentane, hexane and its each
From isomers and/or their mixtures；
The activator is tetrahydrofuran, diethylene glycol, dimethyl ether or tetramethylethylenediamine；
Length/footpath (L/D) of the twin-screw extrusion reaction unit (5) is than being 48-100, and screw diameter is φ 25- φ 150, described
Swivel nut and respective threaded rod, constitute 8 functional areas in order：Transportation section area (5-1) → conversion zone area (5-2) → vacuum flashing section area
(5-3) → terminate section area (5-4) → preceding devolatilization section area (5-5) → rear devolatilization section area (5-6) → pump boost section area (6) die head pelletizing
Section area (8).
5. according to the block copolymer of fragrant alkene any claim 1-2, conjugated diene and epoxides, it is characterised in that
The block copolymer can be used as base material and rubber plastic modified material through percutaneous drug delivery patch agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710200610.XA CN107057005A (en) | 2017-03-30 | 2017-03-30 | A kind of block copolymer of fragrant alkene, conjugated diene and epoxides and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710200610.XA CN107057005A (en) | 2017-03-30 | 2017-03-30 | A kind of block copolymer of fragrant alkene, conjugated diene and epoxides and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107057005A true CN107057005A (en) | 2017-08-18 |
Family
ID=59601837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710200610.XA Pending CN107057005A (en) | 2017-03-30 | 2017-03-30 | A kind of block copolymer of fragrant alkene, conjugated diene and epoxides and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107057005A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522196A (en) * | 2021-08-04 | 2021-10-22 | 南京元初科技有限公司 | Intelligent monitoring system and intelligent monitoring method for preparation of block copolymer of aromatic hydrocarbon, conjugated diene and epoxide |
| CN115073724A (en) * | 2021-03-10 | 2022-09-20 | 华南理工大学 | Olefin and epoxide block copolymerization method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101142247A (en) * | 2005-03-17 | 2008-03-12 | 陶氏环球技术公司 | Pseudo-block copolymers and process employing chain shuttling agent |
| CN104434884A (en) * | 2014-11-05 | 2015-03-25 | 大连理工大学 | Dual-channel hot-melt pressure-sensitive adhesive for transdermal medicine delivery patch and preparation method thereof |
| CN104449488A (en) * | 2014-11-05 | 2015-03-25 | 大连理工大学 | Grafted styrene series thermoplastic elastomer-based hot melt pressure sensitive adhesive and preparation method thereof |
| CN104449494A (en) * | 2014-11-05 | 2015-03-25 | 大连理工大学 | SIS-b-PEO hot-melt pressure-sensitive adhesive and preparation method thereof |
| CN104706624A (en) * | 2015-03-10 | 2015-06-17 | 北京化工大学 | Drug-loading pressure-sensitive adhesive patch using plant oil containing traditional Chinese medicines as plasticizer and preparation method of patch |
-
2017
- 2017-03-30 CN CN201710200610.XA patent/CN107057005A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101142247A (en) * | 2005-03-17 | 2008-03-12 | 陶氏环球技术公司 | Pseudo-block copolymers and process employing chain shuttling agent |
| CN104434884A (en) * | 2014-11-05 | 2015-03-25 | 大连理工大学 | Dual-channel hot-melt pressure-sensitive adhesive for transdermal medicine delivery patch and preparation method thereof |
| CN104449488A (en) * | 2014-11-05 | 2015-03-25 | 大连理工大学 | Grafted styrene series thermoplastic elastomer-based hot melt pressure sensitive adhesive and preparation method thereof |
| CN104449494A (en) * | 2014-11-05 | 2015-03-25 | 大连理工大学 | SIS-b-PEO hot-melt pressure-sensitive adhesive and preparation method thereof |
| CN104706624A (en) * | 2015-03-10 | 2015-06-17 | 北京化工大学 | Drug-loading pressure-sensitive adhesive patch using plant oil containing traditional Chinese medicines as plasticizer and preparation method of patch |
Non-Patent Citations (1)
| Title |
|---|
| 高盼: "含聚环氧乙烷嵌段极性化SIS的制备", 《万方数据库》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073724A (en) * | 2021-03-10 | 2022-09-20 | 华南理工大学 | Olefin and epoxide block copolymerization method |
| CN115073724B (en) * | 2021-03-10 | 2023-07-18 | 华南理工大学 | Method for block copolymerization of olefin and epoxide |
| CN113522196A (en) * | 2021-08-04 | 2021-10-22 | 南京元初科技有限公司 | Intelligent monitoring system and intelligent monitoring method for preparation of block copolymer of aromatic hydrocarbon, conjugated diene and epoxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1643016A (en) | Novel block copolymers and method for making same | |
| CN107057005A (en) | A kind of block copolymer of fragrant alkene, conjugated diene and epoxides and preparation method thereof | |
| CN109957253A (en) | A kind of thermoplastic elastic material and preparation method thereof for coating glass fiber enhanced nylon | |
| JPS6341106A (en) | Novel manufacture of rubber composition using cavity-transfer-mixer | |
| KR20140001916A (en) | Elastomeric block copolymers with a star-shaped molecular architecture, said star-shaped molecular architecture having at least two different star arms | |
| CN103194159B (en) | Hot-melt pressure-sensitive adhesive and preparation method thereof | |
| CN104327347A (en) | High-molecular bonding resin used for non-PVC medical transfusion bag and preparation method thereof | |
| JP2005501172A5 (en) | ||
| CN106008858A (en) | Preparation method of epoxy soybean oil compatilizer for polyolefin composite material | |
| CN103289604A (en) | Hot melt adhesive containing modified attapulgite and preparation method thereof | |
| CN103289606A (en) | Hot melt adhesive used for shoe and preparation method thereof | |
| CN107814944A (en) | Copolymer and preparation method and application | |
| CN103289607A (en) | Hot melt adhesive for aluminium alloy material and preparation method of hot melt adhesive | |
| CN109082000A (en) | A kind of composite of water-proof coiled material and preparation method thereof of in situ reactive compatibilization synthesis | |
| CN101798433A (en) | Non-PVC material for medical infusion products and preparation method thereof | |
| CN111499813B (en) | Method for preparing high-flow AES resin by adopting continuous bulk method | |
| CN104341670A (en) | Toughening master batch | |
| CN108117854A (en) | A kind of line plastic-steel tube special bonding resin and preparation method thereof | |
| CN107513132A (en) | A kind of high melt strength polypropylene material and preparation method thereof | |
| CN108929481A (en) | Modification regeneration polypropylene prepares the expandable injection molding composite material and its manufacturing method of high fondant-strength | |
| CN110157373A (en) | A kind of contact intelligent card base and chip package non-solvent Hot melt adhesive tape | |
| CN112812250B (en) | Preparation method of styrene thermoplastic elastomer | |
| CN108395492A (en) | - 1,4 content carboxyl-terminated polybutadiene liquid rubber of high-cis and end carboxyl polyethylene and preparation method thereof | |
| CN108017833A (en) | A kind of preparation method of high-modulus high impact resistance polypropylene resin | |
| CN103740185B (en) | A kind of atactic copolymerized polypropene coating material |
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 |