CN86100925A - The crosslinked preparation of extending - Google Patents
The crosslinked preparation of extending Download PDFInfo
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- CN86100925A CN86100925A CN 86100925 CN86100925A CN86100925A CN 86100925 A CN86100925 A CN 86100925A CN 86100925 CN86100925 CN 86100925 CN 86100925 A CN86100925 A CN 86100925A CN 86100925 A CN86100925 A CN 86100925A
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- extension product
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Abstract
Make the crosslinked method of extruding extension product by polyethylene or other suitable polymers.The feed hopper that polymer is added screw extruder.Polymer is heated and fusion when the machine barrel by screw extruder.A kind of liquid-state silicon hydride compounds that contains modified vinyl functional silane, the material that produces free radical and condensation catalyst injects the polymer of fusion through metering, the polymer of fusion is mixed equably with the liquid-state silicon hydride compounds, mixture is extruded through extrusion die, formed extension product.Be subjected to the effect of moisture and heat again, till the crosslinked polymer in extension product.The present invention also comprises the equipment of a cover realization said method.
Description
The manufacturing of the extension product that the present invention relates to extrude, cable and the pipe of making by the crosslinked carbochain polymer of hydrolysis class unsaturated silane particularly, but be not these, the manufacture method of this series products of past is polymer to be produced under the situation that the material of free radical exists at peroxide and so on work with hydrolysis class unsaturated silane, makes the material of grafting be subjected to the effect of moisture, heat and silanol condensation catalyst then.Be applicable to reagent existing narration in 3,646, No. 155 United States Patent (USP)s delivering on February 29th, 1972 of this method.After this patent was delivered, people recognized this method and also be applicable to multiple polymers except being applicable to polyethylene that this specification is mentioned and modified poly ethylene.The example of these other polymer of class has haloflex and various olefin copolymer, and they all can be processed in this way, and does not need all strict in all cases reaction condition that above-mentioned United States Patent (USP) proposes of following when adopting method of the present invention.In the method for above-mentioned patent, polyethylene mixes with an organosilicon derivates under the situation of antioxidant and peroxide existence, and chemical interaction takes place.The purpose of this operation be silane free radical " grafting " to the Hi-fax chain.The grafting effect takes place in polyethylene and organosilicon derivates at a touch, but product with must carry out drying before suitable catalyst (must store respectively) mixes.Make crosslinked graft copolymer and catalyst mix then, extrude the product of gained on cable or be extruded into suitable extension product.
It is crosslinked then to place hot water or saturated vapor to carry out extension product, and this step operation may need a few hours, depends on the temperature of thickness and the water or the steam of insulating barrier.
The method that 4,117, No. 195 United States Patent (USP)s authorizing people such as PetersWarbrick that on September 26th, 1978 delivered are introduced has been done improvement to said method.This method is incorporated in grafting and admixture in the single stepping, and has saved and carried out in advance this step of non-granulated processed.In the method, polyethylene or another kind can carry out crosslinked suitable polymer with hydrolysis class unsaturated silane and add in the screw extruder with food ingredient by metering, and food ingredient then is made up of hydrolysis class unsaturated silane, the material that can produce free radical and silanol condensation catalyst.All these compositions all mix in the machine barrel of extruder with polymer, and the temperature of mixture is elevated to is enough to make silylation to be grafted on the polymer.Then make the mixture fusion and from extruder, extrude, form the shaped article that extends, make this product be subjected to the effect of moisture then and crosslinked by extrusion die.
4,117, though the method for No. 195 United States Patent (USP)s than 3,646, the method for No. 155 United States Patent (USP)s improves to some extent, and still has many shortcomings.For example, this method needs expensive screw extruder, and this is that very long machine barrel can make just that material has in machine barrel that time enough mixes because extruder needs, fusion, homogenizing and grafting.For example, to need a length/diameter ratio be that the extruder of 28: 1 or 30: 1 just can make and can extrude and crosslinked fusion and the polymer that mixed for this method.It is generally acknowledged that one of reason is that liquid injects machine barrel or feed hopper with solid material before the polymer heating, heat very unstablely, therefore begin fusion or before the fusion uneven grafting effect takes place just substantially at polymer.
Except above-mentioned shortcoming, the method for 4,117, No. 195 United States Patent (USP)s also needs the device of very expensive mensuration dosage, because each food ingredient all must make food ingredient and polymer keep proper proportion by the careful extruder that is metered into.
Another shortcoming that process is arranged earlier is that the manufactory that adopts this method needs to buy, stores and handle many kinds of components.
The present invention has overcome the shortcoming of above-mentioned prior art.The present invention is a kind of method of making the extruded product of crosslinked extension, and it comprises the polymer of polyethylene and so on by being metered into each step of screw extruder feed hopper, but is not limited only to this.All polymer of being announced in 3,646, No. 155 and 4,117, No. 195 United States Patent (USP)s all are applicable to method of the present invention.The polymer that adds feed hopper is taked the ball shape usually, also can take powder-form.No matter take which kind of form, polymer after adding extruder all by the screw conveyer of extruder, by the machine barrel of extruder.Simultaneously with the polymer heating, till its whole fusions or whole substantially fusion.After the polymer fusion, be that the liquid-state silicon hydride compounds (this material is sold by the Union Carbide Corporation of Connecticut State Danbury) of SILCAT R is expelled in the molten polymer with a kind of trade mark.This compound will be done more detailed explanation below.Molten polymer and liquid-state silicon hydride compounds are promoted to enter mixer by the screw rod of extruder, and it can be the part of extruder, or its extension.With behind the liquid-state silicon hydride compounds injection molten polymer the two being mixed, make mixture pass through extrusion die then, make the product that is stretched of required net shape.After this, 4,117, No. 195 and 3,646, No. 155 United States Patent (USP)s as mentioned above are described, make extension product be subjected to the effect of moisture and heat, so just make the polymer generation in the extension product crosslinked.
Adopt method of the present invention, can extrude and crosslinked fusion and the polymer that mixed for making, the length/diameter of used extruder is than only needing 20: 1, and this is than above-mentioned 4, the required length/diameter of the method for 117, No. 195 United States Patent (USP)s is than much smaller.
The liquid-state silicon hydride compounds is Union Carbide Corporation's production and selling of Connecticut State Danbury, and its brand name is SILCAT R.According to the said firm's explanation, this is a kind of modified vinyl functional silane that contains peroxide and condensation catalyst, and its physical property is as follows:
The physical aspect transparency liquid
120 ℃ of boiling points (760 millimetres of mercury) (248)
Flash-point (ASTMD-29 open cup test method) 31 ℃ (88)
206 ℃ of natural temperatures (ASTMD-268-58T) (403)
Proportion (25 ℃/25 ℃) 0.970～0.974
Viscosity (20 ℃) 0.8cs
Color (Gardner) 1
According to the explanation of Union Carbide Corporation, SILCAT R must be stored in the container of sealing, divide to invade to prevent water, must attention prevent to bring malaria into container when from bucket it being extracted.The said firm's suggestion adopts drying tube or blanket of nitrogen to prevent mixing of water branch.The said firm advises further that also SILCAT R will use draughty local the processing, must not or shine fire near spark, and because it has potential reactivity, storage temperature must not be higher than 40 ℃.
The said firm recommends this compound to can be used for 4,117, the method for No. 195 United States Patent (USP)s, so people infer the functional components and 4,117 of this compound, and it is identical that No. 195 United States Patent (USP)s are announced.
Though claims of the application's latter end specifically noted the invention main contents and apply for a patent clearly, believe by accompanying drawing of the present invention is carried out following explanation and must have a better understanding the present invention.
Fig. 1 is for realizing the front view of a set of equipment that method of the present invention designs, and a part is a profile.
Fig. 2 is a plane of seeing that part of equipment in the past from the 2-2 line direction of Fig. 1.
Fig. 3 is the part figure that realizes the another kind of equipment of this method.
Fig. 4 is the exploded perspective illustration of the mixer of equipment.
Figure 1 shows that used whole devices or the equipment of method of the present invention of realizing.One screw rod 12 is housed on the extruder 10 among the figure, and screw rod can rotate in machine barrel 14, passes through extruder barrel so that polymer is transmitted from feed hopper 18.Must be pointed out that the screw rod 12 shown in the figure is 4,341, the sort of potential barrier screw rod (barrier ScreW) shown in No. 474 United States Patent (USP)s, but extruder screw of the present invention do not leave no choice but the potential barrier type can not.
Around machine barrel 14, a lot of heaters 16 are housed,, make polymer fusion by machine barrel so that essential heat to be provided.This equipment also is equipped with the feed hopper feeder, in order to add polymer, generally use the ball shaped polymer, but also available powdery sometimes.The details of feed hopper feeder is not a part of the present invention, knows technically, does not therefore need here to be described in more detail.
As shown in Figure 1, machine barrel 14 is equipped with flange 23 at its port of export, carries mixing arrangement 22 to be connected on the flange cavity type with bolt.The rotor 54(of this device is as shown in Figure 1) closely be connected with screw rod 12, it can be rotated with screw rod.Yet, as the back to point out, this drive connection is not necessary for the present invention.Rotor 54 rotates in shell or stator 52, and its effect is being mixed to the polymer here by screw conveyer.When extruder turns round, add polymer just fusion fully before the end of the flight that arrives screw rod of the ball shape of feed hopper 18.
Equipment of the present invention also is provided at molten polymer and sends into the device that die cavity conveying blender injects the liquid-state silicon hydride compounds molten polymer before.This device contains the holder 28 of a dress liquid-state silicon hydride compounds.The liquid-state silicon hydride compounds is transported to injection port 44 in shell or the stator 52 by pipeline 29, just in time enters die cavity at polymer and delivers to the there before carrying mixer.Liquid-state silicon hydride compounds supply system has the suction pressure of a suction gauge 30 with measuring diaphragm measuring pump 32, and the diaphragm measuring pump is used for the liquid-state silicon hydride compounds is transported to injection port 44 from holder 28.Disposed an accumulator 34 on the later pipeline of pump 32, its effect is to accumulate the excessive liquid-state silicon hydride compounds that pump 32 is aspirated, and supplies this excessive liquid-state silicon hydride compounds when pump 32 carries out the pulse running.That is to say that accumulator 34 can be eliminated the pulse suction of pump 32 and send effect to supply the liquid-state silicon hydride compounds of stable predetermined amount of flow.
One flow sensor 36 is arranged after accumulator,, also have an injection pressure table 38, in order to the flow through pressure of silane compound of pipeline 29 of measurement in order to measure the flow velocity of liquid-state silicon hydride compounds.Injection pressure table dirty a stop valve 40, manual-lock when being suitable for not working are arranged.
The liquid-state silicon hydride compounds is extracted out from holder 28, is transported to injection port 44 by pipeline 29 and through stop valve 40 with by flexible hose 42.Injection port 44 is equipped with check valve, is only permitted that the liquid-state silicon hydride compounds flows into that die cavity is carried in blender shell or the stator, this is to preventing molten polymer and flow into flexible hose 42 and pipeline 29 being necessary.
As seen from Figure 2, polymer carries blender 22 to extrude from die cavity, enters a right angle feed die 24, and this die head is to be connected to die cavity with bolt to carry on the flange 26 of blender.Make cable 46 by the right angle feed die, its surface, area-covered just wrap or coated polymer 48.
Now want the device of key diagram 1 how to work.Suitable polymers is added feed hopper 18 by feed hopper feeder 20.As noted above such, polymer can be powdery or ball shape.Screw rod 12 mat transmission devices (not illustrating in the drawings) and rotating are so that forward polymer along machine barrel 14.Heater 16 provides heat with melt polymer, makes polymer fusion fully before the end of the flight that arrives screw rod or flange 23.The liquid-state silicon hydride compounds is expelled in the molten polymer by injection port 44, makes the mixture of polymer and liquid-state silicon hydride compounds enter die cavity conveying blender 22 then.The liquid-state silicon hydride compounds is mixed when carrying blender by die cavity uniformly with mixture of polymers.In right angle feed die 24, the mixture of polymer and liquid-state silicon hydride compounds forms insulating barrier 48 around cable 46, be that cable and polymer rely on a suitable die head by angle coupling, this die head is the part of right angle feed die and the thickness that decision is coated to the polymer on the cable.
Figure 3 shows that another kind of alternative connected mode of die cavity conveying blender and extruder barrel.Fig. 3 is its plane, comprises die cavity conveying blender 50, and the longitudinal axis extension of this blender and the longitudinal axis of extruder screw 12 meet at right angles.But the work that this angle is installed hereto is not crucial.Rotor 54 is installed on the armature spindle 56, and the rotor the tip of the axis is equipped with pulley 58.Pulley 58 is driven by pulley 60 and belt 62 by motor 64.Adopt such scheme just can make die cavity carry the rotating speed of blender rotor different with the rotating speed of extruder screw 12.Make polymer and liquid-state silicon hydride compounds obtain better to have the best of control to mix.Can't see the injection port of liquid-state silicon hydride compounds among Fig. 3, this is because Fig. 3 is the plane of cut-away section.Injection port with the liquid-state silicon hydride compounds be expelled to flange 23 in abutting connection with and the die cavity that is arranged in after the end of extruder screw 12 carry blender.Molten polymer is distributed to die cavity by flow distributor 66 and carries in the blender with the liquid-state silicon hydride compounds.The two mixes in blender, sends into right angle feed die 24 then as depicted in figs. 1 and 2.
The exploded perspective illustration that Fig. 4 carries blender for die cavity, among the figure, stator 52 comprises two sympetalous parts, links together around rotor 54 usefulness bolts.Stator and rotor all have a lot of depressions, and they cooperatively interact to guarantee the abundant mixing of polymer and silane compound.The details of this blender is not a part of the present invention.Die cavity carries the details of blender to introduce to some extent in No. 8030586 UK Patent Application, G.M.Gale that its device was delivered on July nineteen eighty-two/August number " Europe rubber magazine " and R.S.Hindmarch close being entitled as of writing " the brilliance prize of RAPRA ' S GliHering Prize(rubber plastic research association) introduction is also arranged in the literary composition.Their two people have made further instruction in being entitled as in " die cavity is carried the application of blender in rubber is extruded " literary composition of delivering on number " elastomer " magazine August nineteen eighty-two again to this device.
Except top said rotary type die cavity is carried the blender, the present invention also can adopt fixed mixer, authorize people's such as Max Huber 3 as on March 18th, 1975 issue, 871, the issue of No. 624 United States Patent (USP)s or on January 15th, 1974 authorize 3 of Max Huber, the type that 785, No. 620 United States Patent (USP)s are introduced.This fixed mixer also can be finished married operation of the present invention, but had better adopt the rotary type die cavity to carry blender.
Make the consumption of the required liquid-state silicon hydride compounds of crosslinked polymer different with the kind of polymer, also different with the desired degree of cross linking, advise that per 200 pounds of polymer adopt 3.30 pounds of liquid-state silicon hydride compounds, perhaps make the liquid-state silicon hydride compounds account for 1.62% of mixture total weight.
Claims (11)
1, make crosslinked extruding and extend the method that produces, it is characterized in that this method comprises:
(a) metering adding in the feed hopper of screw extruder (machine barrel is arranged and traverse the screw rod of machine barrel total length) is a kind of can be with containing modified vinyl official energy alkane silicon, the material that produces free radical and the crosslinked polymer of liquid-state silicon hydride compounds of condensation catalyst;
(b) with the machine barrel of polymer transmission by extruder;
(c) the heated polymerizable thing makes its fusion when transmitting the machine barrel of polymer by screw extruder;
(d) metering contains the liquid-state silicon hydride compounds of modified vinyl functional silane, the material that produces free radical and condensation catalyst and it is expelled in the polymer of fusion.
(e) above-mentioned silane compound and molten polymer are mixed to obtain uniform mixture;
(f) said mixture is extruded by extrusion die, formed the extension product of required net shape.
(g) make above-mentioned extension product be subjected to the effect of moisture till above-mentioned crosslinked polymer.
2, by the crosslinked method of extruding extension product of the described manufacturing of claim 1, wherein polymer adds the feed hopper of extruder with ball shape form.
3, by the crosslinked method of extruding extension product of the described manufacturing of claim 1, wherein polymer passes through described extruder by a screw conveyer, this screw rod has a solid guide groove and a fused mass guide groove, the two is separated by the potential barrier flight, is transmitted through the machine barrel of extruder when polymer and is collected in the fused mass guide groove during fusion.
4, by the crosslinked method of extruding extension product of the described manufacturing of claim 1, wherein the liquid-state silicon hydride compounds all is expelled in the polymer after the fusion substantially at described polymer.
5, by the crosslinked method of extruding extension product of the described manufacturing of claim 1～4, wherein liquid-state silicon hydride compounds and polymer are to carry in the blender at a rotary type die cavity earlier to mix, and mixture are extruded again.
6, make the crosslinked equipment of extruding extension product, it is characterized in that this equipment comprises:
(a). screw extruder, it by machine barrel, traverse the machine barrel total length and formed in order to the screw rod that transports polymer with in order to the feed hopper of accepting polymer;
(b). polymer is added the device of screw extruder feed hopper;
(c). heater, be used for adding the machine barrel of hot extruder, make polymer fusion when transporting by screw rod by machine barrel;
(d). the metering device of scheduled volume crosslinking additives and with the device of above-mentioned additive injection in the molten polymer;
(e). be configured on the extruder barrel, injected the molten polymer of crosslinking additives and made above-mentioned polymer and the device of additive mixing in order to acceptance;
(f). the mixture of above-mentioned polymer and additive is shaped with the extrusion die of the extension goods that obtain desired net shape;
(g). above-mentioned extension product is contacted with moisture so that crosslinked device to take place.
7, by the crosslinked equipment of extruding the extension goods of the described manufacturing of claim 6, wherein the device of mixed polymer and described additive is that a rotary type type is carried mixture.
8, by the crosslinked equipment of extruding the extension goods of the described manufacturing of claim 7, wherein the rotary type die cavity carries blender to comprise a stator and a rotor, and rotor is by extruder screw driving work.
9, extend the equipment of goods by crosslinked the extruding of the described manufacturing of claim 7, wherein the rotary type die cavity carries blender to comprise that the extension of the longitudinal axis of a stator and a rotor, rotor meets at right angles with the longitudinal axis of screw rod, and above-mentioned rotor drives with screw rod and has nothing to do.
10, by the crosslinked equipment of extruding extension product of the described manufacturing of claim 6, the device that wherein mixes described polymer and described additive is a fixed mixing arrangement.
11, by the crosslinked equipment of extruding extension product of the described manufacturing of claim 6, the length/diameter ratio of wherein said screw extruder is about 20: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86100925 CN86100925A (en) | 1986-02-05 | 1986-02-05 | The crosslinked preparation of extending |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86100925 CN86100925A (en) | 1986-02-05 | 1986-02-05 | The crosslinked preparation of extending |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86100925A true CN86100925A (en) | 1987-08-26 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86100925 Pending CN86100925A (en) | 1986-02-05 | 1986-02-05 | The crosslinked preparation of extending |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN86100925A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457420C (en) * | 2002-10-31 | 2009-02-04 | 雷奥两合股份公司 | Extrusion of peroxidic cross-linkable molded plastic parts |
| CN104227864A (en) * | 2013-06-19 | 2014-12-24 | 中国石油化工股份有限公司 | Extruding machine head |
-
1986
- 1986-02-05 CN CN 86100925 patent/CN86100925A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457420C (en) * | 2002-10-31 | 2009-02-04 | 雷奥两合股份公司 | Extrusion of peroxidic cross-linkable molded plastic parts |
| CN104227864A (en) * | 2013-06-19 | 2014-12-24 | 中国石油化工股份有限公司 | Extruding machine head |
| CN104227864B (en) * | 2013-06-19 | 2016-09-14 | 中国石油化工股份有限公司 | Cross-head |
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