CN1012372B - Polyvinyl chloride compound and method of manufacturing said compound - Google Patents
Polyvinyl chloride compound and method of manufacturing said compoundInfo
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- CN1012372B CN1012372B CN 88104444 CN88104444A CN1012372B CN 1012372 B CN1012372 B CN 1012372B CN 88104444 CN88104444 CN 88104444 CN 88104444 A CN88104444 A CN 88104444A CN 1012372 B CN1012372 B CN 1012372B
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- polyvinyl chloride
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Abstract
The present invention discloses a granular polyvinyl chloride compound having both optimal mechanical property and good surface finish during extrusion molding, and also discloses a method for preparing the excellent compound.
Description
The present invention relates to prepare the polyvinyl chloride batch mixing, more specifically say it is a kind of novel polyvinyl chloride batch mixing of preparation.
The polyvinyl chloride batch mixing is to be basic raw material with the polyvinyl chloride (PVC) RESINS and to contain various additive, for example stablizer, filler and impact improving agent, and its consumption will make this batch mixing reach the desired correct balanced property of the processor that is supplied.Raw material can be with the form supply of the Powdered blend of polyvinyl chloride (PVC) RESINS and additive, but more commonly with the form supply of particulate material.
Suspension method polyvinyl chloride (PVC) is commonly referred to be a kind of amorphous polymer, but known it have 5-10% degree of crystallinity.PVC has various morphology grade, and macroscopic powdery granule (its particle diameter is about the 100-150 micron) then is called fine particle (grains).Each fine particle is to be formed by the about 1 micron primary particle set of particle diameter.Express in a simplified manner, in the process of preparation batch mixing, heat is provided and applies shearing action to polyvinyl chloride resin and additive so that original PVC fine particle is broken into littler primary particle, and these entities can be fused together, thereby form a kind of continuous morphology matrix material that contains the additive of distribution.
When temperature raise, the polyvinyl chloride chain promptly unclamped, and become to have flowability, and when cooling off later on, they just can form a kind of more orderly structure again.This orderly alignment is called secondary crystal.Along with temperature rises, this ordered region enlarges rapidly, and is expanded into a kind of network in certain narrow temperature.This networks development degree just is called the fusibility of this kind PVC.When melting degree was high, extension of network was a kind of snappiness melt with regard to shape in whole polyvinyl chloride matrix.
When improving processing temperature, improved the mechanical properties of resulting polyvinyl chloride batch mixing, for example, improved impact and tensile strength.In order to possess favorable mechanical character, it is essential forming some networks, but general receptible view is when high processing temperature at present, and the variation of shock feature is through a maximum value.When this point, believe that those primary particles break fully, thereby form a kind of glassy matrices.But in practice, add man-hour at industrial preparation PVC composition batch mixing and extrusion molding, rare situation that reaches this point.
In the process of preparation polyvinyl chloride batch mixing, the size of the shearing action that is applied is depended in the morphologic change that is taken place in polyvinyl chloride (PVC) RESINS.It was that fragmentation becomes primary particle before forming network owing to secondary crystal that the high shear process process can make fine particle.Shear in the technological process low, primary particle can disappear before this fine particle border disappears.Though narrate as top, the network of secondary crystallite can be expanded fast in narrow temperature, the high shear process process generally can improve the degree of extension of network, i.e. fusibility.
Available several method is estimated fusibility, and still, general method commonly used has three kinds.First kind is the rheology method, and this method is under the fixed temperature of control, and the material sample is forced to push through a mould with constant rate of speed.It is relevant with the fusibility of this sample that this sample is forced to push through the required pressure of this mould.The fusibility of sample is high more, and the pressure that is recorded is just high more so.For example, use a Macklow-Smith rheometer, for the PVC batch mixing that does not add softening agent, the pressure that records can be in the 180-320 kilograms per centimeter
2(piston speed 70 mm/min).At A.GONZE, P.49 PLASTICA VOL 24, has narrated this kind technology in 1971.
The method of second kind of mensuration batch mixing fusibility is to adopt opticmicroscope with the naked eye to observe.With one of this a kind material material grain swelling in acetone solvent (poor solvent of a kind of PVC) earlier, apply shearing action then and observe at microscopically.At this moment, all more weak combinations that this batch mixing is consolidated are all broken, but the secondary crystal of existing high-sequential is not destroyed.Assess its fusibility from the size of viewed this structure, the size of this structure is big more, and the fusibility of this batch mixing is just high more so.For a kind of PVC batch mixing that does not add softening agent, the size of the melting structure of the sample that melting degree is not high is about 5 * 5 microns, and the sample that melting degree is very high then can be greatly to 400 * 600 microns.At D.A.HEMSLEY, R.P.HIGGS, and AMIADONYE, POLYMER COMMUNICATIONS, VOL 24, P.103, narrated this kind measuring method in 1983.
The third method of measuring the batch mixing fusibility is a thermal analysis system, and this method can be measured the amount of secondary crystal body.Can try to achieve the required heat of this crystallite of fusing from the area of melting peak, the fusibility of this heat and this sample has direct relation.Generally speaking, for a kind of PVC batch mixing that does not add softening agent, the required heat △ H of this microcrystal of fusion is every gram PVC 0.5-12.0 Jiao Er.At M.GILBERT, D.A.HEMSLEY, and A.MIADONYE, PLAST.RUBB.PROCESSING AND APPLICATIONS, VOL3 has narrated this kind thermoanalysis technology in P.343.1983.
In general, be favorable mechanical character and good extrusion molding performance and surface smoothness quality should be combined to the major requirement of the PVC batch mixing that is used for extrusion molding.
In order to obtain favorable mechanical character, the network of secondary crystallite is fully expanded.But, can improve the elastic memory of this kind material like this and increase the scope in secondary crystal zone, and under the situation of the PVC that does not add softening agent, when extrusion molding, will cause surface irregularity.In addition, along with the raising of fusibility, a kind of batch mixing of extrusion molding institute energy requirement has also increased, thereby the extrusion molding tooling cost is improved.So, PVC must be formulated into a kind of batch mixing of intermediate degree, thereby take into account good extrusion molding performance and qualified mechanical properties.
Preparation PVC batch mixing has two kinds of traditional methods.First method is to adopt high-shear batch-type mixing machine, prepares batch mixing with two roller roller refining machines then, and is made into sheet, and then cooling and the side's of being cut into grain.Generally can be made into the very batch mixing of homogeneous with this method.But,, need to use a lot of labor forces because this is a kind of batch-type method.
The problem that in the preparation batch mixing, adopts roller refining method to bring, special because be semi-batch process and make labor force's expense very high, meaned that the preparation of present PVC batch mixing generally adopts the continous way mixer to carry out.In this continuous processing, in the mixer machine barrel of heating, will do mixed material fusion by the effect of one or more screw rod, force then to push through a die head and be cut into pellet.
In these conventional batch mixing compound methods, be difficult to the control fusibility, in the narrow narrow temperature range of this kind network fast development because this process is to carry out.In this temperature range, temperature will obtain melting degree batch mixing very inequality as long as change a little.More difficult control fusibility in continuous processing than in semi-batch process is because in mixer inherent design, very little along the variation of the temperature of screw/barrel cross section different positions and shearing action.Will make the indefinite goods of quality change so be supplied to the batch mixing of processor.
Therefore, when adopting traditional method preparation PVC batch mixing, the homogeneous batch mixing that has the particular melt degree to make be need control meticulously, good extrusion molding performance and qualified machinery and physical properties obtained man-hour thereby can add by processor at next step.Generally speaking, for the PVC that does not add softening agent, the specific fusibility of this kind belongs to moderate.When this kind melting degree, as viewed with microscope, melting structure (being the secondary crystal district) has the shape of rule, and size is about 50 microns.The structure of this kind size and dimension can guarantee that this batch mixing has good extrusion molding performance, and makes the extrudate with qualified surface smoothness quality.Disadvantageously, when this medium fusibility, might not reach best physical properties (promptly for the PVC batch mixing that does not add softening agent).Therefore, in the actually operating of using conventional formula mixer, be difficult to accomplish correctly and take into account, thereby can not often reach best character.
In order to obtain to have the PVC batch mixing of optimal mechanical character, the network of secondary crystallite must be expanded fully.So batch mixing is just prepared in the temperature range that network is almost completely expanded, thereby further than carrying out under the low rate.The result can obtain fusibility polyvinyl chloride batch mixing extremely uniformly.But as explained earlier, this type of material is owing to the elastomeric melt that is produced is difficult to carry out extrusion molding (this elasticity is to be produced by big secondary crystal expansion area).
Under high fusibility condition, as adopting acetone swelling and shearing and viewed with opticmicroscope, melting structure has very high length-to-diameter ratio and size greater than 100 * 200 microns.For the good extrudate of surface smoothness, found that these structures must have the shape of rule and be preferably size is the 10-40 micron, but, size is also permitted to 100 microns structure greatly.But the structure of these reduced sizes can keep the high degree of order of inherent, that is the secondary crystal degree.
Obviously, except the requirement of homogenizing mixture with particular melt degree, importantly, the polyvinyl chloride batch mixing that has prepared should contain the additive of good distribution.The effect that the morphology of this grain pattern by this kind polymkeric substance produces, mean that the polyvinyl chloride and the difference of other polymkeric substance of great majority are the character of the finished product, on criticality more, depend on the interaction of used additive, processing equipment used and these two kinds of factors.
The objective of the invention is to prepare a kind of PVC particulate state batch mixing, it not only has best mechanical properties, and also obtains surface of good smooth finish when extrusion molding, and a kind of method for preparing the good batch mixing of this kind is provided.
According to an aspect of the present invention, a kind of method for preparing the polyvinyl chloride batch mixing, the blend composition that comprises a kind of polyvinyl chloride (PVC) RESINS of preparation and additive, this blend composition is sent into a mixer, make this blend composition in this machine, melt and reach high fusibility, utilize an enhancing mixed device immediately the size of melting structure in this polyvinyl chloride batch mixing to be reduced then.
The advantage of this method is to obtain best mechanical properties by the scope of the height melting zone of control secondary crystal, and this batch mixing still has good extrusion molding processing characteristics simultaneously.This enhancing mixed device can guarantee the uniform mixing of additive, can also guarantee the fusibility of this batch mixing.
This enhancing mixed device preferably can repeat repeatedly the structure in the polyvinyl chloride melt to be segmented and remix again, thereby makes the size of this melting structure be reduced to the 10-100 micron, and 10-40 micron preferably.
In general, has the polyvinyl chloride granules meeting of high fusibility because the size of its melting structure surpasses 100 microns so that have a kind of extrusion molding performance that does not meet the requirements.Effect by means of this kind enhancing mixed device is decreased to less than 100 microns the size of this kind melting structure, can obtain good extrusion molding performance.
Be preferably, the condition in control mixer and the enhancing mixed device makes that when measuring with thermal analysis system, this batch mixing has △ H at least
AThe fusibility of=4.5 Jiao Er/gram polyvinyl chloride.In the time will preparing the rigid polyvinyl chloride batch mixing, implement these conditions and suit.
The scheme of another kind of available choosing is that the condition in control mixer and the enhancing mixed device makes that when measuring with thermal analysis system, this batch mixing has △ H at least
AThe fusibility of=3.5 Jiao Er/gram polyvinyl chloride.In the time will preparing the soft PVC batch mixing, implement these conditions and suit.
Adopting the cavity of being narrated in the specification sheets of No. the 930939th, a kind of English Patent to transmit mixing machine (Cavity Transfer Mixer) suits as this enhancing mixed machine.
According to another aspect of the present invention, a kind of polyvinyl chloride batch mixing that comprises polyvinyl chloride (PVC) RESINS and additive when the use heat assay, has △ H at least
AThe fusibility of=4.5 Jiao Er/gram polyvinyl chloride, the shape of melting structure are that size is the 10-100 micron uniformly, and homogeneous disperses and the additive of distribution.
The combination of high fusibility and undersized melting structure can cause having the polyvinyl chloride batch mixing of fabulous mechanical properties and good extrusion molding character.
Suitable additive can have stablizer, lubricant, impact improving agent, processing aid, filler and pigment.
Below further specify the present invention with example and accompanying drawing, accompanying drawing is the step synoptic diagram of a method according to the present present invention.
In order to prepare a kind of polyvinyl chloride batch mixing, the adulterant 1 adding mixer 2 with polyvinyl chloride (PVC) RESINS and additive suitably disposes an enhancing mixed device 4 at the mixer discharge end, as shown in FIG..This mixing device should be able to be by segmentation and remix become small construction (the ideal situation size is at the 10-40 micron) but can not change the high fusibility originally of this material, the scope of mechanically dwindling the high melting zone of secondary crystal more over and over again with this melting structure.This kind device also should be PVC to be had distribute and the mixing machine of dissemination, so that obtain fusibility and additive all is uniform mixture.Preferred enhancing mixed device is to transmit mixing machine (Cavity Transfer Mixer) by a kind of cavity that RAPRA Technology Ltd is developed, this equipment is to be used for masterbatch in the distribution polyethylene batch mixing, describes to some extent in the specification sheets of No. the 9030939th, English Patent.The processing conditions of batch mixing preparation depends on the prescription of used mixer type and this batch mixing.In general, with the barrel section temperature of mixer and other processing conditionss, promptly spiro rod rate etc. is set up, and makes the melt temperature that makes reach 120-210 ℃.The melt of gained is forced by the die head of attaching in mixing device 4 discharge port places, cut off and cooling by granulation unit mahine 6 then.
In order to guarantee that these less PVC structures can not remerge, and be to be retained in the final product actually,, must produce specific mixing effect in the final stage of this batch mixing process.
All can prepare this kind polyvinyl chloride batch mixing with hard or soft PVC.
By the prepared PVC batch mixing of present method, can comprise stablizer, lubricant, impact improving agent, processing aid, filler and pigment, and have very high fusibility; According to the mensuration of the thermal analysis system of measuring fusibility, when using flexible PVC preparation batch mixing, fusibility △ H
A＞3.5 Jiao Er/gram PVC, when using the hard PVC preparation, fusibility △ H
A＞4.5 Jiao Er/gram PVC.This novel mixing has the uniform melting structure of shape, and its magnitude range is 10-40 micron (employing resembles the method for optical microscopy one class of acetone swelling and shearing and measures).It is desired much smaller that its structure size is compared this fusibility; Usually can obtain the structure of size range at the 100-200 micron.At last, measure distribution of additives and dispersion effect that this novel mixing tool is fabulous according to optical microscopy.
Further the manufacturers of this polyvinyl chloride batch mixing of processing will find, this PVC batch mixing that provides with pellet form from the dispersion and the distribution of fusibility and additive, is a kind of typical case very uniformly usually.Fusibility by the batch mixing of present method preparation is very high, and the high fusibility of this kind can make end article have best mechanical properties, promptly high impact and tensile strength.In addition, because the melting structure of the size of the rule of the about 10-40 micron of existence size in this melt, so this batch mixing has good extrusion molding performance.Usually, when adopting traditional continous way mixing equipment, become a kind of elastomeric melt owing to the size of melting structure surpasses 100 microns (being measured by the optical microscopy that the acetone swelling is sheared), the PVC batch mixing of high fusibility will produce a kind of extrusion molding performance that does not meet the requirements.Therefore, former, can only between the optimal mechanical character of end article and good extrusion molding performance, take into account.
The shortcoming of those batch mixings before this PVC batch mixing has overcome.
The following stated example is intended to illustrate the result by method preparation PVC batch mixing of the present invention, but does not limit the present invention.
Example
By about 75% polyvinyl chloride (PVC) RESINS, 11% pearl filler, and titanium dioxide and other habitual additives, prepare a kind of hard PVC batch mixing.Adopt two kinds of different methods to prepare this kind batch mixing:
Use a retrograde rotation engaging double-screw rod extruding machine (50 millimeters of screw diameters) to prepare sample " A " and " B " of different fusibilities in a usual manner.Select processing conditions, sample " A " is had, and medium/low melt degree (gelationization) sample " B " then has high fusibility.
An equipped cavity transmits mixing machine (CTM) on the used identical extruding machine in method 1.The operating method of this CTM meets the requirement of above-mentioned a kind of suitable enhancing mixed device.Use this extruding machine then, and adopt the batch mixing condition of being narrated in the 6th to 7 page in this specification sheets identical to prepare sample " C " and " D " with method 1 through repacking.
Use a single-bolt type extruding machine (30 millimeters of screw diameters) of when application PVC batch mixing manufactures a product, habitually practising to carry out extrusion molding processing then.
Control sample " A " with low-middle fusibility is though have qualified surface smoothness, and shown mechanical properties fails to give full play to.On the other hand, given play to mechanical properties preferably after having control sample " B " extrusion molding of high fusibility, but because the snappiness essence of this batch mixing, its surface smoothness is nonconforming.
The mixture samples " C " and " D " that prepare by method of the present invention are although the used condition difference that is mixed all obtains the batch mixing (adopting rheometer measurement and determine with dsc method) of high fusibility.The extrudate that these high fusibility samples can obtain having fabulous mechanical properties has surpassed the sample that adopts conventional method preparation batch mixing, even has surpassed the close sample (being sample " B ") of fusibility.But, the qualitative evaluation of extrudate is shown the surface smoothness of sample " C " and " D " has surpassed the prepared extrudate of the high fusibility batch mixing that conventional method for mixing is prepared (sample " B ").
Show through microscopic evaluation that for method 2 prepared high fusibility samples (being sample " C " and " D ") shape of their melting structure and size are all fairly regular.The shape of these melting structures almost is a square, and size is approximately 30 microns.These melting structures are with different by the prepared high fusibility sample (being sample " B ") of method 1, and they are that bigger size (about 100-150 micron) is arranged, and shape is quite irregular.
To method 2(sample " C " and " D ") reduction of prepared viewed this kind elastic memory of sample, from the littler proof that also obtains of diameter of the prepared high fusibility sample " B " of its particle diameter ratio method 1.
Claims (5)
1, a kind of polyvinyl chloride batch mixing that comprises polyvinyl chloride (PVC) RESINS and additive when measuring with thermoanalysis technology, has △ H at least for the soft PVC batch mixing
AThe fusibility of=3.5 Jiao Er/gram polyvinyl chloride and for the rigid polyvinyl chloride batch mixing, have △ H at least
AThe fusibility of=4.5 Jiao Er/gram polyvinyl chloride has the melting structure that is of a size of 10-100 micron and uniform shapes, and the additive of homodisperse and distribution.
2, a kind of polyvinyl chloride batch mixing by claim 1, wherein adding can be stablizer, lubricant, impact improving agent, processing aid, filler and pigment.
3, a kind of method for preparing a kind of polyvinyl chloride batch mixing in the claim 1 to 2, this method comprises the blend of preparation polyvinyl chloride (PVC) RESINS and additive, this blend is added a mixer, in this machine, reach melt temperature 120-210 ℃, make this blend fusing and reach high fusibility, then immediately by the enhancing mixed effect, with the melting structure in this polyvinyl chloride melt over and over again again the segmentation and remix reduce the size of the melting structure in this polyvinyl chloride batch mixing, be about the 10-100 micron thereby reach diameter.
4, a kind of method by claim 3, wherein this enhancing mixed process size of continuing to the melting structure in the polyvinyl chloride melt is reduced to till the 10-40 micron.
5, a kind of method by claim 3, this method are included in to be used a cover die head after this enhancing mixed process this melt further is shaped to the rod shape, should hold in both hands then that bar cools off and cut-out, to form the pellet of this kind polyvinyl chloride batch mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88104444 CN1012372B (en) | 1987-01-21 | 1988-07-16 | Polyvinyl chloride compound and method of manufacturing said compound |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878701268A GB8701268D0 (en) | 1987-01-21 | 1987-01-21 | Preparation of compounded polyvinyl chloride |
| CN 88104444 CN1012372B (en) | 1987-01-21 | 1988-07-16 | Polyvinyl chloride compound and method of manufacturing said compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1039608A CN1039608A (en) | 1990-02-14 |
| CN1012372B true CN1012372B (en) | 1991-04-17 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88104444 Expired CN1012372B (en) | 1987-01-21 | 1988-07-16 | Polyvinyl chloride compound and method of manufacturing said compound |
Country Status (1)
| Country | Link |
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| CN (1) | CN1012372B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110303615A (en) * | 2019-07-24 | 2019-10-08 | 南通中联工业发展有限公司 | A kind of preparation method of highly elastic polyvinyl chloride product |
-
1988
- 1988-07-16 CN CN 88104444 patent/CN1012372B/en not_active Expired
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| Publication number | Publication date |
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| CN1039608A (en) | 1990-02-14 |
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