CN108164669A - The production technology and its process units of a kind of thermoplastic polyurethane - Google Patents
The production technology and its process units of a kind of thermoplastic polyurethane Download PDFInfo
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- CN108164669A CN108164669A CN201711441367.7A CN201711441367A CN108164669A CN 108164669 A CN108164669 A CN 108164669A CN 201711441367 A CN201711441367 A CN 201711441367A CN 108164669 A CN108164669 A CN 108164669A
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- screw extruder
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- thermoplastic polyurethane
- isocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
Abstract
The invention discloses a kind of production technologies of thermoplastic polyurethane, the technique uses the extrusion reaction of three rank screw extruders, it will include the raw material components of macromolecular polyol, small molecule chain extender, isocyanates and auxiliary agent, by controlling the pretreatment of each raw material components and injection mode, the reaction condition of each rank screw extruder, to prepare thermoplastic polyurethane.The production technology of the present invention effectively controls, enhances synthetic reaction, makes the thermoplastic polyurethane of preparation can not only take into account high viscosity, few gel point and relatively low YI values, but also can accelerate reaction process, reduces the maturation period, improves yield.The process units of the present invention is connected the three rank screw extruders to be formed by three screw extruders by specific configuration, reaction rate and the extent of reaction can effectively be adjusted, improve viscosity, avoid the generation of gel point, prevent material colour changed into yellow, the final control realized to properties of product, obtains the thermoplastic polyurethane for having ideal performance.
Description
Technical field
The present invention relates to thermoplastic polyurethane material's technical field more particularly to a kind of production technologies of thermoplastic polyurethane
And its process units.
Background technology
Thermoplastic polyurethane is a kind of macromolecular material containing carbamate groups or urethane urea groups in strand
It is referred to as, because it has the good characteristics such as good wearability, resistant of high or low temperature, biocompatibility, high tenacity, widely should
For bio-medical material, furniture building materials, electric wire, aerospace, shipbuilding, automobile, textile garment, rail traffic etc.
In all trades and professions.The processing method of thermoplastic polyurethane can be divided into extrusion, injection, curtain coating, blowing, coating etc., but no matter make
The requirement which kind of processing to have comparison high processability, gel point, color of thermoplastic polyurethane material etc. with.
At present there are mainly two types of the production methods of thermoplastic polyurethane, the first is reaction kettle method, and second is to squeeze out instead
Ying Fa.Reaction kettle method is easy to control reaction rate and gel point, but this method belongs to intermittent operation, and it is certain special to be only applied to
The synthesis for the thermoplastic polyurethane that field uses.Extrusion reaction is owned by France in consecutive production, and without solvent, and it is flexible to have operation
With control simple advantage, application than wide, but extrusion reaction technique there are a technical barrier to get to thermoplasticity
Polyurethane cannot meet downstream application to gel point, color and highly viscous specific demand.Patent CN200710015771.8 draws
Enter a kind of post curing measure, the extent of reaction is strengthened by post curing, reduce the maturation period of thermoplastic polyurethane, but this method
The gel point and color characteristics of product cannot fundamentally be improved.
Invention content
To solve the shortcomings of the prior art, the present invention provides a kind of production technology of thermoplastic polyurethane, the works
Skill uses three rank screw extruders, and passes through the pretreatment for controlling each raw material components and injection mode, each rank screw extruder
Reaction condition to control, strengthen reaction, makes the thermoplastic polyurethane of preparation both have higher viscosity, few gel point, compared with
Low YI values, and reaction process can be accelerated, the maturation period is reduced, improves yield.
To achieve the above object, the present invention provides a kind of production technology of thermoplastic polyurethane, include the following steps：
A, each raw material components are obtained；The raw material components include macromolecular polyol, small molecule chain extender, isocyanates,
And auxiliary agent；The auxiliary agent include antioxidant, lubricant, light stabilizer, catalyst, anti-hydrolysis agent, antistatic agent, processing aid,
At least one of pigment, delustering agent, anti-blocking agent, antiseptic, fire retardant；
B, extrusion reaction technique is carried out using three rank screw extruders：
B1, macromolecular polyol, small molecule chain extender, isocyanates, part of auxiliary are pre-processed respectively, then noted
Enter into the first rank screw extruder, squeezed out under the conditions of 150~250 DEG C of set temperature, 200~500rpm of setting speed
Reaction, second-order screw extruder is injected by extrudate；One kind in the pretreatment mode selection following methods；
B1-1, antioxidant of the fusing point less than 100 DEG C, lubricant in macromolecular polyol and auxiliary agent are pre-mixed, will mixed
System is preheated to 100~200 DEG C；Small molecule chain extender is preheated to 40~150 DEG C；Isocyanates is preheated to 40~100 DEG C；
Then macromolecular polyol mixed system, small molecule chain extender, the isocyanates after preheating are injected into respectively via bottler placer
In first rank screw extruder；
B1-2, macromolecular polyol and part isocyanates are prepared into prepolymer, by fusing point in auxiliary agent less than 100 DEG C
Antioxidant, lubricant are added in prepolymer, and prepolymer mixed system is preheated to 100~200 DEG C；Small molecule chain extender is pre-
Heat is to 40~150 DEG C；Remaining isocyanates is preheated to 40~100 DEG C；Then by the prepolymer mixed system, small after preheating
Molecule chain extender, isocyanates are injected into via bottler placer in the first rank screw extruder respectively；
B1-3, antioxidant of the fusing point less than 100 DEG C, lubricant and small molecule in macromolecular polyol and auxiliary agent are expanded
Chain agent is pre-mixed, and macromolecular polyol mixed system is preheated to 100~200 DEG C；Isocyanates is preheated to 40~100 DEG C；
Then macromolecular polyol mixed system, the isocyanates after preheating are injected into the first rank Screw Extrusion via bottler placer respectively
In machine；
B2, it other antioxidants, lubricant and the catalyst in auxiliary agent is added to second-order screw rod through sprue squeezes
Go out in machine, the extrudate with the first rank screw extruder is in 150~250 DEG C of set temperature, setting speed 100~240rpm conditions
Extrudate is injected into third rank screw extruder by lower carry out extrusion reaction；
B3, other auxiliary agents in raw material components are added to through sprue in third rank screw extruder, with second-order spiral shell
The extrudate of bar extruder completes extrusion reaction under the conditions of 150~230 DEG C of set temperature, 80~200rpm of setting speed, obtains
To extrudate be thermoplastic polyurethane.
The thermoplastic polyurethane production technology of the present invention, using the extrusion reaction technique of three rank screw extruders, passes through limit
Determine the pretreatment condition of macromolecular polyol, small molecule chain extender and isocyanates, adjust the reactivity of raw material, and then control
The generation of reaction rate processed and gel point, to influence the color of finished product；By limiting macromolecular polyol, small molecule chain extension
Agent and the injection mode of isocyanates, effectively control reaction rate, and adjust the macromolecular chain structure of thermoplastic polyurethane；It is logical
The injection mode for limiting auxiliary agent is crossed, efficiently plays the effect of different auxiliary agents, while avoiding the auxiliary agent from failing, further adjusts molecule
The structure of chain.Under the premise of the pretreatment of each raw material components and injection mode is limited, then coordinate the reaction of each rank screw extruder
Condition need to carry out the requirement of different disposal to adapt to the synthetic reaction process differential responses stage, anti-so as to effectively control, strengthen
Should, the thermoplastic polyurethane of preparation is made both to have taken into account high viscosity, few gel point, relatively low YI values, is completed to properties of product
Control, obtains the thermoplastic polyurethane for having ideal performance, and can improve the extent of reaction, reduces the maturation period, improves yield.
As the restriction to said program, the macromolecular polyol includes polyester polyol, polyether polyol, gathers
At least one of olefin type polyalcohol, polycarbonate polyol, polyacrylate polyols.
Polyester polyol is to prepare a kind of most common polyalcohol of thermoplastic polyurethane, usually by small molecule binary
Acid, small molecule diol reaction are prepared, the polyester polyol obtained in addition with hydroxy fatty acid or lactone autohemagglutination.Choosing
Polyester polyol molecular weight is generally 600~6000, preferably 800~4000, most preferably 1000~3000.
Common small molecule binary acid has 1,4- succinic acid, 1,6- adipic acids, 1,8- suberic acids, 1,9- azelaic acids, 1,10-
Decanedioic acid, 1,12 dodecanedioic acid, phthalic acid, terephthalic acid (TPA) etc..Common small molecule dihydric alcohol has ethylene glycol, 1,
2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 2- methyl-1,3-propanediols, neopentyl glycol, 1,4- butanediols, 2- methyl-
1,4- butanediols, 1,5- pentanediols, 3- methyl-1s, 5- pentanediols, 3,3- dimethyl -1,5- pentanediols, 1,6-HD, 1,7-
Heptandiol, 1,8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols, 1,4 cyclohexane dimethanol etc..Common lactone has in oneself
Ester.
Polyether polyol is to prepare the another kind of thermoplastic polyurethane to commonly use polyalcohol, and common polyether polyol has
Polyethylene oxide polyol, polyoxypropylene polyol, polytetrahydrofuran polyol, polyethylene oxide-propylene oxide copolymer are more
First alcohol, polyethylene oxide tetrahydrofuran polyol, polypropylene oxide tetrahydrofuran polyol.The polyether-type of selection is more
First alcohol molecular weight is generally 600~5000, preferably 800~3000, most preferably 1000~2000.
Polyolefin polyols are common end hydroxy butadiene type polyalcohol, hydroxy-teminal butadiene-acrylonitrile compolymer
Object, hydroxy-teminal butadiene-styrol copolymer etc..The polyolefin polyols molecular weight of selection is generally 1000~5000, excellent
It is selected as 2000~4000.
Polycarbonate polyol refers in molecular backbone containing the carbonate group (- O-COO -) and the end of the chain repeated
For a kind of polymer of hydroxyl (- OH), aliphatic, aromatic series and mixed type three categories can be divided into according to the difference of backbone structure,
What wherein application study was most is aliphatic polycarbonate diol.
As the restriction to said program, the small molecule chain extender is the terminal hydroxy group dihydric alcohol that molecular weight is 40~400.
Common small molecule chain extender has the trihydroxylic alcohols such as glycerine, trimethylolpropane；Ethylene glycol, 1,2- propylene glycol, 1,3-
Propylene glycol, 1,3 butylene glycol, 2- methyl-1,3-propanediols, neopentyl glycol, 1,4- butanediols, 2- methyl-1s, 4- butanediols, 1,
5- pentanediols, 3- methyl-1s, 5- pentanediols, 3,3- dimethyl -1,5- pentanediols, 1,6-HD, 1,8- ethohexadiols, 1,9- nonyls
Glycol, 1,10- decanediols, 1,4-CHDM, hydroquinone two hydroxy ethyl ether, diglycol, two three second two of contracting
The dihydric alcohols such as alcohol, dipropylene glycol, tripropylene glycol；And cyclohexanol, cyclohexanemethanol, n-butanol, normal propyl alcohol, ethyl alcohol etc.
Monohydric alcohol.
As the restriction to said program, the isocyanates includes aliphatic isocyanates, alicyclic isocyanate, virtue
At least one of fragrant race's isocyanates.
Common aliphatic isocyanates have 1,4- butane diisocyanates, 1,6- hexamethylene diisocyanates, L- to rely
Propylhomoserin diisocyanate；Common alicyclic isocyanate have isophorone diisocyanate, 1,4- cyclohexane diisocyanates,
1- methyl -2,4- cyclohexane diisocyanates, 1- methyl -2,6- cyclohexane diisocyanates, dicyclohexyl methyl hydride diisocyanate
Ester；Common aromatic isocyanate have toluene di-isocyanate(TDI), paraphenylene diisocyanate, methyl diphenylene diisocyanate,
1,5- naphthalene diisocyanates, 3,3 '-dimethyl -4,4 '-biphenyl diisocyanate etc..
Prepare the auxiliary agent that thermoplastic polyurethane often uses have antioxidant, lubricant, light stabilizer, catalyst, anti-hydrolysis agent,
Antistatic agent, processing aid, pigment, delustering agent, anti-blocking agent, antiseptic, fire retardant etc..
Wherein, common antioxidant has Hinered phenols, hindered amines, thio esters, phosphite ester kind antioxidant etc..It is common
Lubricant have fatty acid, fatty acid ester, fatty acid acyl amine, fatty acid salt, cover courage wax class, annular terephthalic acid (TPA)
Butanediol esters, silicone oil series lubricant agent etc..Common light stabilizer has hindered amines, benzophenone, azimidobenzene class, triazine
Series lubricant agent etc..Common catalyst has organic tin, titanate ester and other metallic salt catalyst etc..It is common
Anti-hydrolysis agent has Carbodiimides, epoxies anti-hydrolysis agent etc..
Meanwhile the present invention also provides the process units of thermoplastic polyurethane, including by three screw extruders through connection
Device is connected the three rank screw extruders to be formed, and the angle of the first rank screw extruder and level ground is 0 °~60 °, described
The angle of first rank screw extruder and second-order screw extruder is 90 °, the second-order, third rank screw extruder and water
The angle of plane earth is 0 °, and the angle of the second-order screw extruder and third rank screw extruder is 0 °~90 °；It is described
Using double screw extruder, the third rank screw extruder uses twin-screw extrusion for first rank, second-order screw extruder
Machine or single screw extrusion machine.
Be plasticized, be sufficiently mixed, energy-efficient purpose for the reaction between raw material components is made to reach reinforcing, it is of the invention with three screw rods
Extruder is by specific configuration and three rank screw extruders of formation of connecting are as reaction unit, is controlled using three rank screw extruders
Early period, mid-term and the later stage of reaction are made, to adapt to the step-reaction polymerization original that thermoplastic polyurethane synthetic reaction process need to follow
Reason, coordinates the increase with the reaction time, reactant molecule amount exponentially increases, and in the different stages of reaction, synthetic reaction
System has the characteristic of completely different viscous systems, realizes and effectively adjusts reaction rate and the extent of reaction, improves viscosity, avoids
The generation of gel point prevents material colour changed into yellow, accelerates reaction and carries out, improves the purpose of yield.
As the restriction to said program, first rank, second-order screw extruder use parallel engagement type in the same direction
Double screw extruder, and have at least one of hybrid element, shearing elements.
As the restriction to said program, the third rank screw extruder uses parallel type double screw extruder.This is double
Screw extruder can be engagement type or be non-engagement type；Can be type in the same direction or incorgruous type.
As the restriction to said program, the first rank screw extruder includes 1~8 section, and the second-order screw rod squeezes
Go out machine and include 5~10 sections, the third rank screw extruder includes 5~10 sections.
Screw extruder can be divided into single screw extrusion machine, double screw extruder and more spiral shells according to the difference of screw rod number
Bar extruder.Double screw extruder is divided into hing surface and non-engagement type according to whether there is engagement in screw rod
Double screw extruder.From screw rod direction of rotation, double screw extruder can be divided into the same direction and Heterodromy double-screw extruder.It presses
Two screw rods axis it is parallel whether twin-screw can be divided into parallel double-screw or conical double screw extruder.Engagement type double spiral shells in the same direction
The screw element of bar extruder can include at least one of three kinds of delivery element, shearing elements and hybrid element elements.
In conclusion technical solution using the present invention, the production technology of the thermoplastic polyurethane of acquisition utilize three rank spiral shells
The extrusion reaction technique of bar extruder, by controlling the pretreatment of each raw material components and injection mode, each rank screw extruder
Reaction condition to control, strengthen reaction, makes the thermoplastic polyurethane of preparation both take into account high viscosity, few gel point, relatively low
YI values, and the extent of reaction can be improved, the maturation period in later stage is reduced, improves yield.The process units of the present invention is by three screw rods
Extruder is connected the three rank screw extruders to be formed by specific configuration, effectively early period, mid-term and the later stage of control reaction, is effectively adjusted
Reaction rate and the extent of reaction are saved, viscosity is improved, avoids the generation of gel point, prevent material colour changed into yellow, it is final to realize to production
The control of moral character energy, obtains the thermoplastic polyurethane for having ideal performance.
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the front view of three rank screw extruder structure diagrams described in the embodiment of the present invention；
Fig. 2 is the vertical view of three rank screw extruder structure diagrams described in the embodiment of the present invention；
Fig. 3 is the side view of three rank screw extruder structure diagrams described in the embodiment of the present invention；
In figure：1st, the first rank screw extruder；2nd, second-order screw extruder；3rd, third rank screw extruder；4th, it connects
Device；The angle of α 1, the first rank screw extruder and ground；The folder of α 2, the first rank screw extruder and second-order screw extruder
Angle；The angle of α 3, second-order screw extruder and third rank screw extruder.
Specific embodiment
Below in conjunction with embodiment, technical scheme of the present invention is clearly and completely described, it is clear that described
Embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field
Those of ordinary skill's all other embodiments obtained without making creative work, belong to protection of the present invention
Range.
Embodiment
The present embodiment is related to the production technology and process units of thermoplastic polyurethane (TPU).
The process units of TPU, including the three rank screw extruders that are formed of being connected by three screw extruders through connector,
Using double screw extruder, third rank screw extruder uses double screw extruder or list for single order, second-order screw extruder
Screw extruder.As shown in Fig. 1 combinations Fig. 2, Fig. 3, the angle of the first rank screw extruder and level ground is 0 °~
60 °, since screw extruder is a kind of equipment of pillar shape, there can be a angle with ground when sideling putting；Described first
The angle of rank screw extruder and second-order screw extruder is 90 °, the second-order, third rank screw extruder and flatly
The angle in face is 0 °, and the angle of the second-order screw extruder and third rank screw extruder is 0 °~90 °；
The process units, on concrete structure, the first rank screw extruder is squeezed using parallel intermeshing twin-screw in the same direction
Go out machine, have at least one of hybrid element, shearing elements, include 1~8 section；The first rank screw extruder is using flat
Row hing surface in the same direction, has at least one of hybrid element, shearing elements, includes 5~10 sections；Described
Three rank screw extruders use parallel type double screw extruder, can be engagement type or non-engagement comprising 5~10 sections
Type can be type in the same direction or incorgruous type.
The preparation of TPU is carried out in above-mentioned process units.
Embodiment one
A kind of preparation of injection molding TPU, production technology are as follows：
A, each raw material components are obtained according to product formula, the raw material components include macromolecular polyol, small molecule chain extension
Agent, isocyanates and auxiliary agent；The auxiliary agent includes antioxidant, lubricant, catalyst, anti-hydrolysis agent, antistatic agent, and pigment disappears
Photo etching, antiseptic, fire retardant；
B, extrusion reaction technique is carried out using three rank screw extruders：
B1, the lubricant that antioxidant of the fusing point less than 100 DEG C, fusing point in macromolecular polyol and auxiliary agent are less than to 100 DEG C
Premixing, 140 ± 20 DEG C are preheated to by mixed system；Small molecule chain extender is preheated to 50 ± 10 DEG C；Isocyanates is preheated
To 60 ± 20 DEG C；Then by after preheating macromolecular polyol mixed system, small molecule chain extender, isocyanates is respectively via filling
Note machine is injected into comprising in 3 sections of the first rank screw extruder；150~200 DEG C of set temperature, setting speed 300~
Extrusion reaction is carried out under the conditions of 400rpm, extrudate is injected into second-order screw extruder；
B2, other antioxidants, lubricant and the catalyst in auxiliary agent are added to through sprue comprising the of 6 sections
In second order screw rod extruder, with the extrudate of the first rank screw extruder 150~200 DEG C of set temperature, setting speed 150~
Extrusion reaction is carried out under the conditions of 200rpm, extrudate is injected into third rank screw extruder；
B3, other auxiliary agents in raw material components are added to through sprue comprising in 10 sections of third rank screw extruder,
It is completed under the conditions of 150~200 DEG C of set temperature, 150~200rpm of setting speed with the extrudate of second-order screw extruder
Extrusion reaction, obtained extrudate are injection molding TPU.
Performance detection is carried out to the injection molding TPU products of acquisition, the performance connotation and detection method being related to are as follows：
Particle YI：For characterizing the color of particle, numerical value is bigger, and representative is more yellow, is detected using X-rite spectroscopes,
About 12g particles are weighed, are put into quartzy transparent utensil, choose reflective-mode test.Different location is chosen, measures 3 times and is averaged
Value.
Fusing point：It is tested using temperature-raising method, weighs particle 1.5g and add in Shimadzu capillary rheology instrument heating furnace, initial temperature is set
It is set to 30 DEG C, heating rate is set as 6 DEG C/min, and it is fusing point to take outflow temperature Tfb.
Fisheye：The number of gel point in thermoplastic polyurethane product is represented, quantity, and the gel point that represents is more, product
Can be poorer, using petrographic microscope in a length of 100mm, width 100mm, thickness is the diameter observed in 100 μm of film
Fine particle number not less than 80 μm.
Dust point：The number of gel point in thermoplastic polyurethane product is represented, digital-to-analogue is more, and gel point is more, properties of product
It is poorer, using petrographic microscope in a length of 100mm, width 100mm, thickness be this diameter observed of film of 2mm not
Fine particle number less than 100 μm.
NCO content：The extent of reaction of thermoplastic polyurethane is represented, numerical value is bigger, and the extent of reaction is lower, more incomplete.
Injection molding TPU properties of product testing results are as shown in table 1：
The physical property of 1 injection molding TPU of table
Explanation：75A represents the shore hardness TPU as 75+/- 2A, 95A and represents shore hardness as 95+/- 2A's in table 1
TPU, 60D represent TPU of the shore hardness as 60+/- 2D, are prepared to be using the present invention；Single-order 95A represents existing
There is the TPU that technology uses shore hardness prepared by the production of single-order screw extruder as 95+/- 2A；Double rank 95A represent the prior art
Use the TPU of shore hardness prepared by twin-screw extruder production for 95+/- 2A.Similar character generation in 2~table of continued 4 afterwards
The meaning of table and so on.
Embodiment two
A kind of preparation of extrusion type TPU, production technology are as follows：
A, each raw material components are obtained according to product formula, the raw material components include macromolecule dihydric alcohol, small molecule chain extension
Agent, isocyanates and auxiliary agent；The auxiliary agent includes antioxidant, lubricant, catalyst, anti-hydrolysis agent, antistatic agent, and pigment disappears
Photo etching, anti-blocking agent, antiseptic, fire retardant；
B, extrusion reaction technique is carried out using three rank screw extruders：
B1, macromolecular polyol and part isocyanates be prepared into prepolymer, the preparation of performed polymer by the prior art into
Row, such as：The temperature of reaction kettle is controlled between 60~90 DEG C, preferably 70~80 DEG C, in a nitrogen atmosphere, by a certain amount of isocyanic acid
Ester is added in reaction kettle, is 1.5 by the ratio between amount of-NCO and-OH substances after its thawing:1 to 2:1, polyalcohol is primary
Or be continuously added drop-wise in reaction kettle and reacted, the extent of reaction is controlled by characterizing the concentration of-NCO in reaction system, directly
It completes just to have obtained performed polymer prepared by polyalcohol and isocyanates to reaction.Prepare isocyanates dosage that performed polymer uses by
Formula determines that is, isocyanates and macromolecular polyol are there are total ratio, and prepare the isocyanates and macromolecular of performed polymer
Polyalcohol is again there are usage ratio, depending on TPU formulas to be prepared.By antioxidant of the fusing point in auxiliary agent less than 100 DEG C, melt
Lubricant of the point less than 100 DEG C is added in prepolymer, and prepolymer mixed system is preheated to 160 ± 20 DEG C；Small molecule is expanded
Chain agent is preheated to 60 ± 10 DEG C；Remaining isocyanates is preheated to 80 ± 20 DEG C；It then will be pre- after preheating using bottler placer
Polymer blend system, small molecule chain extender, isocyanates are injected into via bottler placer comprising 5 sections of the first rank Screw Extrusion respectively
In machine；Extrusion reaction is carried out under the conditions of 150~200 DEG C of set temperature, 250~350rpm of setting speed, extrudate is injected
To second-order screw extruder；
B2, other antioxidants, lubricant and the catalyst in auxiliary agent are added to through sprue comprising the of 8 sections
In second order screw rod extruder, with the extrudate of the first rank screw extruder 150~200 DEG C of set temperature, setting speed 160~
Extrusion reaction is carried out under the conditions of 210rpm, extrudate is injected into third rank screw extruder；
B3, other auxiliary agents in raw material components are added to through sprue comprising in 10 sections of third rank screw extruder,
It is completed under the conditions of 150~220 DEG C of set temperature, 100~150rpm of setting speed with the extrudate of second-order screw extruder
Extrusion reaction, obtained extrudate are extrusion type TPU.
Performance detection is carried out to the extrusion type TPU products of acquisition, the performance connotation and detection method being related to are same as above, detection knot
Fruit is as shown in table 2：
The physical property of 2 extrusion type TPU of table
MI represents the melt viscosity of TPU in table 2, and numerical value is smaller, and viscosity is bigger.
Embodiment three
A kind of preparation of curtain coating type TPU, production technology are as follows：
A, each raw material components are obtained according to product formula, the raw material components include macromolecular polyol, small molecule chain extension
Agent, isocyanates and auxiliary agent；The auxiliary agent includes antioxidant, lubricant, catalyst, anti-hydrolysis agent, antistatic agent, and pigment disappears
Photo etching, anti-blocking agent, antiseptic, fire retardant；
B, extrusion reaction technique is carried out using three rank screw extruders：
B1, by TPU formulary requirements to be prepared, by antioxidant of the fusing point less than 100 DEG C in macromolecular polyol and auxiliary agent,
Lubricant of the fusing point less than 100 DEG C and small molecule chain extender premixing, 180 are preheated to by macromolecular polyol mixed system
±20℃；Isocyanates is preheated to 80 ± 20 DEG C；Then by the macromolecular polyol mixed system, different after the preheating after preheating
Cyanate is injected into via bottler placer comprising in 5 sections of the first rank screw extruder respectively；In 160~240 DEG C of set temperature, set
Determine to carry out extrusion reaction under the conditions of 350~450rpm of rotating speed, extrudate is injected into second-order screw extruder；
B2, other antioxidants, lubricant and the catalyst in auxiliary agent are added to through sprue comprising the of 10 sections
In second order screw rod extruder, with the extrudate of the first rank screw extruder 160~200 DEG C of set temperature, setting speed 150~
Extrusion reaction is carried out under the conditions of 200rpm, extrudate is injected into third rank screw extruder；
B3, other auxiliary agents in raw material components are added to through sprue comprising in 6 sections of third rank screw extruder, with
The extrudate of second-order screw extruder is completed to squeeze under the conditions of 150~220 DEG C of set temperature, 100~150rpm of setting speed
Go out reaction, obtained extrudate is extrusion type TPU.
Performance detection is carried out to the curtain coating type TPU products of acquisition, the performance connotation and detection method being related to are same as above, detection knot
Fruit is as shown in table 3：
The physical property of 3 curtain coating type TPU of table
Example IV
A kind of preparation of blown type TPU, production technology are as follows：
A, each raw material components are obtained according to product formula, the raw material components include macromolecular polyol, small molecule chain extension
Agent, isocyanates and auxiliary agent；The auxiliary agent includes antioxidant, lubricant, catalyst, anti-hydrolysis agent, antistatic agent, and pigment disappears
Photo etching, anti-blocking agent, antiseptic, fire retardant；
B, extrusion reaction technique is carried out using three rank screw extruders：
B1, antioxidant of the fusing point less than 100 DEG C, lubricant in macromolecular polyol and auxiliary agent are pre-mixed, by mixture
System is preheated to 180 ± 20 DEG C；Small molecule chain extender is preheated to 60 ± 10 DEG C；Isocyanates is preheated to 80 ± 20 DEG C；Then
Macromolecular polyol mixed system, small molecule chain extender, isocyanates after preheating is injected into via bottler placer comprising 5 respectively
In first rank screw extruder of section；It is squeezed out under the conditions of 160~200 DEG C of set temperature, 350~450rpm of setting speed
Reaction, second-order screw extruder is injected by extrudate；
B2, other antioxidants, lubricant and the catalyst in auxiliary agent are added to through sprue comprising the of 8 sections
In second order screw rod extruder, with the extrudate of the first rank screw extruder 160~180 DEG C of set temperature, setting speed 150~
Extrusion reaction is carried out under the conditions of 200rpm, extrudate is injected into third rank screw extruder；
B3, other auxiliary agents in raw material components are added to through sprue comprising in 10 sections of third rank screw extruder,
It is completed under the conditions of 150~220 DEG C of set temperature, 100~150rpm of setting speed with the extrudate of second-order screw extruder
Extrusion reaction, obtained extrudate are blown type TPU.
Performance detection is carried out to the blown type TPU products of acquisition, the performance connotation and detection method being related to are as follows, detection knot
Fruit is as shown in table 4：
The physical property of 4 blown type TPU of table
It, can be strong using twin-screw extruder by the data of 1~table of table 4 as it can be seen that compared to using single-order screw extruder
Change the reaction of polyurethane, fisheye number and NCO content is made all to be reduced, the control of fisheye is typically the rotating speed by improving screw rod
It realizes, but improve screw speed to reduce the viscosity of melt later, highly viscous product can not be made, therefore cannot strengthen most
The whole extent of reaction.The three rank Screw Extrusion reaction process of the present invention, by the pretreatment and the injection side that limit each raw material components
Formula can substantially reduce fisheye number and NCO content, avoid the generation of gel point；Simultaneously by adjusting the rotating speed of screw rod, that is, carry
The rotating speed of two rank screw rods before height reduces the rotating speed of third rank screw rod, non-crystal point and highly viscous TPU products is had both to prepare,
But also reaction process can be accelerated, the maturation period in later stage is reduced, improves yield.
In conclusion the production technology of thermoplastic polyurethane disclosed by the invention, utilizes the extrusion of three rank screw extruders
Reaction process by controlling the pretreatment of each raw material components and injection mode, the reaction condition of each rank screw extruder, is effectively controlled
It makes, enhance synthetic reaction, the thermoplastic polyurethane of preparation is made not only to have taken into account high viscosity, few gel point, relatively low YI values, but also
The extent of reaction can be improved, reduces the maturation period in later stage, improves yield.The process units of the present invention is pressed by three screw extruders
Specific configuration is connected the three rank screw extruders to be formed, and can effectively be adjusted reaction rate and the extent of reaction, be avoided gel point
It generates, prevents material colour changed into yellow, the final control realized to properties of product obtains the thermoplastic poly ammonia for having ideal performance
Ester.
Claims (8)
1. a kind of production technology of thermoplastic polyurethane, which is characterized in that include the following steps：
A, each raw material components are obtained；The raw material components include macromolecular polyol, small molecule chain extender, isocyanates and help
Agent；The auxiliary agent include antioxidant, lubricant, light stabilizer, catalyst, anti-hydrolysis agent, antistatic agent, processing aid, pigment,
At least one of delustering agent, anti-blocking agent, antiseptic, fire retardant；
B, extrusion reaction technique is carried out using three rank screw extruders：
B1, macromolecular polyol, small molecule chain extender, isocyanates, part of auxiliary are pre-processed respectively, are then injected into
In first rank screw extruder, carry out squeezing out under the conditions of 150~250 DEG C of set temperature, 200~500rpm of setting speed anti-
Should, extrudate is injected into second-order screw extruder；One kind in the pretreatment mode selection following methods；
B1-1, antioxidant of the fusing point less than 100 DEG C, lubricant in macromolecular polyol and auxiliary agent are pre-mixed, by mixed system
It is preheated to 100~200 DEG C；Small molecule chain extender is preheated to 40~150 DEG C；Isocyanates is preheated to 40~100 DEG C；Then
Macromolecular polyol mixed system, small molecule chain extender, isocyanates after preheating is injected into first via bottler placer respectively
In rank screw extruder；
B1-2, macromolecular polyol and part isocyanates are prepared into prepolymer, fusing point in auxiliary agent is less than to 100 DEG C of antioxygen
Agent, lubricant are added in prepolymer, and prepolymer mixed system is preheated to 100~200 DEG C；Small molecule chain extender is preheated to
40~150 DEG C；Remaining isocyanates is preheated to 40~100 DEG C；Then by after preheating prepolymer mixed system, small molecule
Chain extender, isocyanates are injected into via bottler placer in the first rank screw extruder respectively；
B1-3, antioxidant, lubricant and the small molecule chain extender that fusing point in macromolecular polyol and auxiliary agent is less than to 100 DEG C
Premixing, 100~200 DEG C are preheated to by macromolecular polyol mixed system；Isocyanates is preheated to 40~100 DEG C；Then
Macromolecular polyol mixed system, isocyanates after preheating is injected into the first rank screw extruder via bottler placer respectively
It is interior；
B2, other antioxidants, lubricant and the catalyst in auxiliary agent are added to second-order screw extruder through sprue
It is interior, with the extrudate of the first rank screw extruder under the conditions of 150~250 DEG C of set temperature, 100~240rpm of setting speed into
Extrudate is injected into third rank screw extruder by row extrusion reaction；
B3, other auxiliary agents in raw material components are added to through sprue in third rank screw extruder, are squeezed with second-order screw rod
The extrudate for going out machine completes extrusion reaction under the conditions of 150~230 DEG C of set temperature, 80~200rpm of setting speed, obtains
Extrudate is thermoplastic polyurethane.
2. the production technology of thermoplastic polyurethane according to claim 1, it is characterised in that：The macromolecular polyol packet
It is polynary to include polyester polyol, polyether polyol, polyolefin polyols, polycarbonate polyol, polyacrylate
At least one of alcohol.
3. the production technology of thermoplastic polyurethane according to claim 1, it is characterised in that：The small molecule chain extender is
Molecular weight is 40~400 terminal hydroxy group dihydric alcohol.
4. the production technology of thermoplastic polyurethane according to claim 1, which is characterized in that the isocyanates includes fat
At least one of fat race isocyanates, alicyclic isocyanate, aromatic isocyanate.
5. a kind of process units of thermoplastic polyurethane, it is characterised in that：Including being connected by three screw extruders through connector
The angle of the three rank screw extruders formed, the first rank screw extruder and level ground is 0 °~60 °, first rank
The angle of screw extruder and second-order screw extruder is 90 °, the second-order, third rank screw extruder and level ground
Angle be 0 °, the angle of the second-order screw extruder and third rank screw extruder is 0 °~90 °；Described first
Rank, second-order screw extruder using double screw extruder, the third rank screw extruder using double screw extruder or
Single screw extrusion machine.
6. the process units of thermoplastic polyurethane according to claim 5, it is characterised in that：First rank, second-order
Screw extruder using parallel hing surface in the same direction, and have in hybrid element, shearing elements at least one
Kind.
7. the process units of thermoplastic polyurethane according to claim 5, it is characterised in that：The third rank Screw Extrusion
Machine uses parallel type double screw extruder.
8. the process units of thermoplastic polyurethane according to claim 5, it is characterised in that：The first rank Screw Extrusion
Machine includes 1~8 section, and the second-order screw extruder includes 5~10 sections, and the third rank screw extruder includes 5~10 sections.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109354999A (en) * | 2018-09-29 | 2019-02-19 | 江苏凯伦建材股份有限公司 | A kind of polyurethane water-proof paint production line |
| CN109355000A (en) * | 2018-09-29 | 2019-02-19 | 江苏凯伦建材股份有限公司 | A kind of process for producing polyurethane water-proof paint |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260367A (en) * | 2010-05-28 | 2011-11-30 | 上海恒安实业有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN102585485A (en) * | 2012-01-06 | 2012-07-18 | 华南理工大学 | Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof |
| CN204844803U (en) * | 2015-07-10 | 2015-12-09 | 珠海市金塑塑料有限公司 | Serial -type third -order on single screw extruder group |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260367A (en) * | 2010-05-28 | 2011-11-30 | 上海恒安实业有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
| CN102585485A (en) * | 2012-01-06 | 2012-07-18 | 华南理工大学 | Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof |
| CN204844803U (en) * | 2015-07-10 | 2015-12-09 | 珠海市金塑塑料有限公司 | Serial -type third -order on single screw extruder group |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109354999A (en) * | 2018-09-29 | 2019-02-19 | 江苏凯伦建材股份有限公司 | A kind of polyurethane water-proof paint production line |
| CN109355000A (en) * | 2018-09-29 | 2019-02-19 | 江苏凯伦建材股份有限公司 | A kind of process for producing polyurethane water-proof paint |
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Application publication date: 20180615 |