CN109483851B - Process for controlling polymer crystallinity in extrusion processing process - Google Patents
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Abstract
The invention relates to the field of polymer crystallinity control, and provides a method for controlling polymer crystallization in an extrusion processing processAnd (4) performing a temperature process. The process for controlling the crystallinity of the polymer in the extrusion processing process comprises the following steps: melting and extruding the crystalline polymer; combining the extruded crystalline polymer melt through a thermal medium to prepare a wire rod of a polymer material, wherein the thermal medium combination comprises n sections of thermal media, and n is a positive integer; the heat medium through which the melt passes is numbered 1, 2, 3 … n in sequence, and the temperature of the corresponding heat medium is T1，T2，T3…Tn. The process heat medium for controlling the crystallinity of the polymer in the extrusion processing process is divided into a plurality of sections, wherein the number of the sections of the heat medium and the specific temperature of each section can be flexibly selected by combining the crystallization behavior, the chemical property, the cost requirement and the like of the material, so that the thermal history of the material after extrusion is controlled, the crystallization of the material is promoted, and the extruded product is ensured to have stable and uniform crystallinity.
Description
Technical Field
The invention relates to the field of polymer crystallinity control, in particular to a process for controlling polymer crystallinity in an extrusion processing process.
Background
At present, the common extrusion process in the field of polymer processing and manufacturing cannot well control the crystallinity of the crystalline polymer. This results in the following: the crystallinity of the final extruded product of crystalline polymers is often uncontrollable, thus leading to unstable or undesirable product properties. In recent years, 3D printing, also called additive manufacturing, has been emerging, and is a class of advanced manufacturing methods based on the principle of layer-by-layer material accumulation that has emerged and developed rapidly in recent 30 years. The material extrusion type 3D printing in the sub-process has been widely applied in recent years due to the advantages of low equipment cost, wide material selection, good performance of the formed part and the like. The material extrusion type 3D printing process is based on the construction of 3D objects by extruding, layer-by-layer stacking and solidifying (e.g. glass transition, crystallization, solvent evaporation, etc.) of materials under pressure in a flow regime (e.g. molten state, solution, etc.). One of the processes widely used in material extrusion type 3D printing is called fused deposition modeling (fused deposition modeling) or fused wire fabrication (fused wire fabrication), and the basic principle is as follows: conveying a thermoplastic macromolecule wire to a high-temperature hot end by using a gear to melt the macromolecule, moving the hot end along the section profile and the filling track of the part under the control of a computer motion control system, extruding the molten material, rapidly solidifying the material, and locally fusing the material with the surrounding material; this process is repeated layer by layer to build up the three-dimensional object.
In the case of a crystalline polymer for melt-bulk molding, the crystallinity of the wire is very important for the printing performance. Meanwhile, a large number of researches prove that the post-treatment thermal process has important influence on the crystallinity of the crystal-form polymer. However, the process for improving the crystallinity through the thermal technique in the existing research has the disadvantages of high cost, requirements on the composition of materials (such as fibers and nanoparticles), complex equipment and process control and great difficulty in practical application. Therefore, the cooling part of the extrusion process, which is common in practical production, usually contains only a heat medium (e.g., cold water) at normal or low temperature, and the purpose is only to rapidly cool the melt. For many crystalline polymers, the conventional process results in poor crystallinity, poor properties, instability, and even internal stress of the final extruded product.
In view of the above, there is an urgent need in the market for a process that can effectively and precisely control the crystallization behavior of crystalline polymers during the extrusion process. The process can be widely used for crystalline polymer extrusion products, and improves the control on the product performance. The process is particularly suitable for preparing crystalline polymer wires for melt-deposition molding.
Disclosure of Invention
The invention aims to provide a process for controlling the crystallinity of a high polymer in the extrusion processing process, wherein the heat medium of the process is divided into a plurality of sections, wherein the number of the sections of the heat medium and the specific temperature of each section can be flexibly selected by combining the crystallization behavior, the chemical property, the cost requirement and the like of a material, so that the thermal history of the material after extrusion is controlled, the crystallization of the material is promoted, and the extruded product is ensured to have stable and uniform crystallinity.
The invention solves the technical problem by adopting the following technical scheme.
The invention provides a process for controlling the crystallinity of a macromolecule in the extrusion processing process, which comprises the following steps:
step S1: melting and extruding the crystalline polymer;
step S2: combining the extruded crystalline polymer melt through a thermal medium to prepare a wire rod of a polymer material, wherein the thermal medium combination comprises n sections of thermal media, and n is a positive integer; the heat medium through which the melt passes is numbered 1, 2, 3 … n in sequence, and the temperature of the corresponding heat medium is T1，T2，T3…Tn。
The process for controlling the crystallinity of the polymer in the extrusion processing process has the beneficial effects that:
(1) the process heat medium is divided into a plurality of sections, wherein the number of the sections of the heat medium and the specific temperature of each section can be flexibly selected by combining the crystallization behavior, the chemical property, the cost requirement and the like of the material, so that the heat history of the extruded material is controlled, the crystallization of the material is promoted, and the extruded product is ensured to have stable and uniform crystallinity;
(2) the material is subjected to online crystallization in a plurality of heat media after being extruded by the process, so that the crystallization of the material is synchronously completed in the extrusion process, no additional post-treatment step is needed, and large draft ratio and complex flow field control are not needed;
(3) the process can be widely applied to various crystalline polymers, and has the advantages of low cost, high yield and easy implementation.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a test curve of a DSC of a common high molecular material with cold crystallization property;
FIG. 2 is a process flow diagram of the present invention for controlling the crystallinity of a polymer during an extrusion process.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The cooling crystallization process of the polymer melt is roughly as follows: the plastic particles are extruded to form a polymer melt, and the microstructure is composed of randomly entangled polymer chains. In the process of cooling the polymer melt at the outlet die, some polymer chains keep a disordered state to form an amorphous area; some polymer chains are regularly arranged to form crystal regions. The ratio of the crystalline region is the crystallinity of the polymer material.
The crystallization of the high molecular material mainly comprises two steps: (1) nucleation, i.e. the formation of crystal nuclei by the polymer chains or other components under certain conditions; (2) and (4) crystal growth, namely regularly arranging high molecular chains around the crystal nucleus to form crystals. For a particular material, there will be a temperature dependence of nucleation and crystal growth, i.e. there will be temperatures T 'and T "(where T' < T") corresponding to the fastest nucleation and fastest crystal growth temperatures, respectively. In the process of cooling the melt, part of the high polymer material can only form crystal nuclei and cannot grow into crystals. This is because when the temperature of the melt is gradually cooled from a high temperature, the melt reaches a temperature around T ″ (the temperature at which crystals grow fastest), and at this time, the molecular chain moves and easily grows crystals, but the melt lacks crystal nuclei for the crystals to adhere and grow, so that no crystallization region is formed in the melt; when the temperature further drops to reach the vicinity of T', a large number of crystal nuclei begin to be formed by the melt, but at the moment and subsequent temperature, the molecular chain segment is difficult to move, and crystals cannot grow out in a regular arrangement around the crystal nuclei. When the cooled material is heated a second time and the temperature reaches around T ", the polymer chains start to grow crystals from the crystal nuclei. This crystallization behavior is generally referred to as cold crystallization, and a polymer material having a cold crystallization behavior may also be referred to as a cold-crystallized polymer. Common cold-crystallizing polymers include: polylactic acid, poly (dimethyl terephthalate), a portion of polyamide, and the like.
The cold crystallization behavior can generally be characterized by Differential Scanning Calorimetry (DSC). The characterization method comprises the following steps:
1. appropriate amounts of sample (usually several milligrams to tens of milligrams) are weighed as required by the particular DSC instrument;
2. the samples were placed in a DSC instrument and measured using the following temperature program:
a. primary temperature rise: heating the sample to a specific temperature T at a constant heating rate (10-20C/min)h，ThAbove the maximum melting point T of the materialmAnd all crystal regions of the material can be completely melted to form a melt;
b. cooling: cooling the sample to a specific temperature T at a constant cooling rate (10-20C/min)l，TlBelow the glass transition temperature T of the materialgAnd can make the material completely turn into solid state without fluidity;
c. secondary heating: reheating the sample to a specific temperature T at a constant temperature rise rate (10-20C/min)h’，Th' above the highest melting point T of the materialmAnd all crystal regions of the material can be completely melted to form a melt. T ish' and ThMay be the same or different;
d. record the heat flow during the first temperature rise, temperature fall and second temperature rise.
Wherein, Th，TlAnd Th' flexible selection can be made for the characteristics of different materials. If the material exhibits a crystallization peak (generally, an exothermic peak at a temperature lower than the melting peak, as shown in fig. 1) having an area not equal to zero during the secondary temperature increase, it can be judged that the material has cold crystallization behavior. The temperature corresponding to the crystallization peak in the secondary heating process is the cold crystallization temperature, Tcold。
T' > T ", or both, of another portion of the polymeric material, nucleation of the material melt during cooling occurs prior to crystal growth, or nucleation and crystal growth occur simultaneously. Such polymers typically do not exhibit a cold crystallization peak, i.e., no significant crystallization peak during the second temperature increase, under testing using the same DSC method as described above. The crystallization peak usually occurs only during the cooling. The temperature corresponding to the crystallization peak during the temperature reduction process can generally be considered as the crystallization temperature, or Tc, of the material.
The following is a detailed description of a process for controlling the crystallinity of a polymer during an extrusion process according to an embodiment of the present invention.
The invention provides a process for controlling the crystallinity of a macromolecule in the extrusion processing process, which comprises the following steps:
step S1: melting and extruding the crystalline polymer; in the above step, the crystalline polymer includes one or more of Polyethylene (PE), polyethylene terephthalate (PET), Polytetrafluoroethylene (PTFE), polypropylene (PP), Polyamide (PA), polybutylene terephthalate (PBT), Polyoxymethylene (POM), polyvinyl chloride (PVC), polyether ether ketone (PEEK), Polyphenylene Sulfide (PPs), polyvinylidene fluoride (PVDF), Polycaprolactone (PCL), polylactic acid (PLA), and a copolymer of any of the above polymers; wherein, the crystalline polymer also comprises one or more of the following components: colorants, pigments, fillers, fibers, plasticizers, nucleating agents, heat/UV stabilizers, processing aids, impact modifiers;
step S2: combining the extruded crystalline polymer melt through a thermal medium to prepare a wire rod of a polymer material, wherein the thermal medium combination comprises n sections of thermal media, and n is a positive integer; the heat medium through which the melt passes is numbered 1, 2, 3 … n in sequence, and the temperature of the corresponding heat medium is T1，T2，T3…Tn. The heat medium is one or more of air blowing, water bath, oil bath, melting low-temperature alloy, high-temperature salt melt, infrared radiation, microwave radiation and alternating magnetic field; among them, when the heat medium is one or more of air blowing, water bath, and oil bath, cost, practicality, and the like are preferable.
Further, in a preferred embodiment of the present invention, the crystalline polymer exhibits a cold crystallization behavior, and the glass transition temperature and the cold crystallization temperature of the crystalline polymer are set to be the same as each otherTg、TcoldThe number n of stages of the heat medium is not less than 2.
Further, in the preferred embodiment of the present invention, in the step S2, the number of stages n of the heat medium is 3 or more.
Further, in the preferred embodiment of the present invention, in the step S2, the temperature T of the heat medium1<T2. The crystallization of the high molecular material mainly comprises two steps: (1) nucleation, i.e. the formation of crystal nuclei by the polymer chains or other components under certain conditions; (2) and (4) crystal growth, namely regularly arranging high molecular chains around the crystal nucleus to form crystals. For a particular material, there will be a temperature dependence of nucleation and crystal growth, i.e., there will be temperatures T 'and T ″ (where T'<T "), corresponding to the temperature at which nucleation is fastest and the temperature at which crystal growth is fastest, respectively. In the process of cooling the melt, part of the high polymer material can only form crystal nuclei and cannot grow into crystals. This is because when the temperature of the melt is gradually cooled from a high temperature, the melt reaches a temperature around T ″ (the temperature at which crystals grow fastest), and at this time, the molecular chain moves and easily grows crystals, but the melt lacks crystal nuclei for the crystals to adhere and grow, so that no crystallization region is formed in the melt; when the temperature further drops to reach the vicinity of T', a large number of crystal nuclei begin to be formed by the melt, but at the moment and subsequent temperature, the molecular chain segment is difficult to move, and crystals cannot grow out in a regular arrangement around the crystal nuclei. When the cooled material is heated a second time and the temperature reaches around T ", the polymer chains start to grow crystals from the crystal nuclei. When T is1<T2In the process, the extruded wire passes through low temperature T1After nucleation, the temperature is relatively high T2Crystal growth is carried out. The cleanliness of the completed nucleated and crystallized wire is higher.
Further, in the preferred embodiment of the present invention, in the step S2, the temperature T of the heat medium1Glass transition temperature TgAnd cold crystallization temperature TcoldThe relationship of (1) is: t isg<T1<Tcold。T1Greater than TgThe polymer melt is not completely converted into a solid state without fluidity, and is less than TcoldCan achieve the second in the subsequent temperature rise processThe cold crystallization temperature T corresponding to the crystallization peak in the secondary heating processcoldAnd then crystallized and grown at a subsequent temperature.
Further, in the preferred embodiment of the present invention, in the step S2, the temperature T of the heat medium2And cold crystallization temperature TcoldThe relationship of (1) is: t iscold–20℃<T2<Tcold+20 ℃. Will T2Is selected at the cold crystallization temperature TcoldNear, the wire is favorable to be at T2Crystal growth at temperature.
Further, in the preferred embodiment of the present invention, in the step S2, the temperature T of the heat medium2And cold crystallization temperature TcoldThe relationship of (1) is: t iscold–10℃<T2<Tcold+10℃。T2The closer to the cold crystallization temperature TcoldThe more favorable the wire is at T2Crystal growth at temperature.
Further, in the preferred embodiment of the present invention, in the step S2, the temperature T of the heat medium2And cold crystallization temperature TcoldThe relationship of (1) is: t iscold–5℃<T2<Tcold+5℃。T2The closer to the cold crystallization temperature TcoldThe more favorable the wire is at T2Crystal growth at temperature.
Further, in the preferred embodiment of the present invention, in the step S2, the relationship between the temperature of the heat medium and the temperature of the heat medium is T1<T2，T3<T2. The extruded wire passes through low temperature T1After nucleation, the temperature is relatively high T2Crystal growth is carried out. The cleanliness of the completed nucleated and crystallized wire is higher. At the slave T2Cooling to T3After which a cooled wire is obtained.
Further, in a preferred embodiment of the present invention, the temperature T of the heat medium is set to be lower than the temperature T of the heat medium3Glass transition temperature TgThe relationship of (1) is: t is3<Tg。T3Temperature below the glass transition temperature TgThe cooling speed is high, and the wire can be completely converted into a solid state without fluidity.
Further, in a preferred embodiment of the present invention, the crystalline polymer does not exhibit a cold crystallization behavior, and the crystallization temperature of the crystalline polymer is TcThe glass transition temperature of the crystalline polymer is Tg。
Further, in the preferred embodiment of the present invention, in the step S2, the number of stages n of the heat medium is not less than 2, and the temperature T of the heat medium is1>T2. In this embodiment, the polymer material is preferably a polymer that does not exhibit cold crystallization behavior.
Further, in the preferred embodiment of the present invention, in the step S2, the temperature T of the heat medium1And a crystallization temperature TcThe relationship of (1) is: t isc–20℃<T1<Tc+20℃。
Further, in the preferred embodiment of the present invention, in the step S2, the temperature T of the heat medium1And a crystallization temperature TcThe relationship of (1) is: t isc–10℃<T1<Tc+10℃。
Further, in the preferred embodiment of the present invention, in the step S2, the temperature T of the heat medium1And a crystallization temperature TcThe relationship of (1) is: t isc–5℃<T1<Tc+5℃。
Further, in the preferred embodiment of the present invention, in the step S2, the heat medium is one or more of air blowing, water bath, oil bath, melting low temperature alloy, high temperature salt melt, infrared radiation, microwave radiation, and alternating magnetic field.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The L1001 polylactic acid material of Suzhou Polycompound high polymer materials Co., Ltd is selected for extrusion processing, and the relevant parameters of the material and the crystallization behavior thereof are obtained by DSC measurement on a DSC-60Plus instrument of Shimadzu. The specific measurement method comprises the following steps: 50mg of the material to be measured is weighed by a high-precision balance, placed in an aluminum crucible, and then an aluminum upper cover is added, and a sample is pressed and placed in an instrument. Temperature raising and lowering program for setting instrumentComprises the following steps: heating from room temperature to 230 deg.C at a speed of 10 deg.C/min, and keeping for 3 min; cooling to 20 deg.C at a speed of 10 deg.C/min, and keeping for 3 min; finally, the temperature is raised to 230 ℃ at the speed of 10 ℃/min, and the experiment is ended. Heat flow data for the entire process was extracted and the relevant temperature of the material was obtained from the curve peak data. And the properties related to the crystallization behavior of the L1001-grade polylactic acid material of Suzhou polycompound polymer materials GmbH are measured as follows: t isg＝61.3℃；Tc(none), no melt crystallization peak; t iscold＝113.5℃；Tm149.5 ℃. According to the detection result, the material has cold crystallization behavior.
The embodiment provides a process for controlling the crystallinity of a polymer in an extrusion process, which comprises the following steps:
step S1: melting and extruding the crystalline polymer;
step S2: the extruded crystalline polymer melt is combined by hot media to prepare a wire rod of a polymer material, wherein the hot media combination comprises 1 section of hot media and 2 sections of hot media, the 1 section of hot media and the 2 sections of hot media adopt water bath and oil bath respectively, and the temperature is T respectively1And T2And T is1<T2. Wherein, Table 1 is T1And T2The temperature relationship of (a).
Table 1 is T1And T2Temperature relationship of
Example 2
The extrusion processing of polylactic acid material of L2001 brand from Suzhou Polyconjugated Polymer materials Ltd was used, and the detection method of example 1 was used, and the material and the relevant parameters of its crystallization behavior were obtained by DSC measurement on DSC-60Plus instrument from Shimadzu. Finally, the correlation between the material and the crystallization behavior is measuredThe quality is as follows: t isg＝56.6℃；Tc＝124.2℃；Tcold＝93.2℃；Tm168.6 ℃. It is seen that the material has both melt and cold crystallization behavior. In the traditional wire rod production process, the melt cooling speed is 50-100 ℃/s, the molecular chain regular arrangement is inhibited by quenching, the melting crystallization behavior is greatly influenced, and the crystallinity in the wire rod is low.
According to the condition that the material has both melt crystallization and cold crystallization behaviors, the embodiment provides the process for controlling the crystallinity of the high polymer in the extrusion processing process, which comprises the following steps:
step S1: melting and extruding the crystalline polymer;
step S2: combining the extruded crystalline polymer melt with hot medium to obtain the wire rod of polymer material, wherein the hot medium combination comprises 1 section of hot medium and 2 sections of hot medium, the 1 section of hot medium adopts water bath, and the water temperature T is1The temperature is 60 ℃, and the functions of melt shaping and rapid nucleation are achieved; 2-stage heat medium also adopts water bath, and the water temperature is T2Wherein 73.2C<T2<113.2 ℃ is used for promoting the link activity and promoting the growth of a crystal region.
Example 3
The extrusion processing of polylactic acid material of L2001 brand from Suzhou Polyconjugated Polymer materials Ltd was used, and the detection method of example 1 was used, and the material and the relevant parameters of its crystallization behavior were obtained by DSC measurement on DSC-60Plus instrument from Shimadzu. The properties of the material related to crystallization behavior were finally measured as follows: t isg＝56.6℃；Tc＝124.2℃；Tcold＝93.2℃；Tm168.6 ℃. It is seen that the material has both melt and cold crystallization behavior. In the traditional wire rod production process, the melt cooling speed is 50-100 ℃/s, the molecular chain regular arrangement is inhibited by quenching, the melting crystallization behavior is greatly influenced, and the crystallinity in the wire rod is low.
According to the condition that the material has both melt crystallization and cold crystallization behaviors, the embodiment provides a process for controlling the crystallinity of a high polymer in an extrusion processing process, which comprises the following steps:
step S1: melting and extruding the crystalline polymer;
step S2: combining the extruded crystalline polymer melt with hot medium to obtain the wire rod of polymer material, wherein the hot medium combination comprises 1 section of hot medium, 2 sections of hot medium and 3 sections of hot medium, the 1 section of hot medium adopts water bath, and the water temperature T is1The effects of melt shaping and rapid nucleation are achieved; 2-stage heat medium also adopts water bath with water temperature T2The method is used for promoting the link activity and promoting the growth of a crystal region; the 3-stage heat medium also adopts water bath with water temperature T3And the cooling effect is achieved.
In this embodiment, the number of stages of the heat medium is 3, but in other embodiments, the number of stages of the heat medium may be n. As shown in FIG. 2, which is a process flow diagram when the number of stages of the heat medium is n, the polymer melt is extruded from the extrusion equipment and then sequentially passes through a temperature T1，T2，T3…TnThe heat medium of (2). The addition of an additional heat medium between any two of the above heat media can realize the process of wire nucleation and crystal growth by adjusting the temperature, and all the additional heat media are possible embodiments of the present invention within the allowable scope of the technology described in the present invention. It should be understood that the present embodiment is also applicable to multi-component polymer blends, such as simultaneously comprising a plurality of polymer compositions having different crystallization behaviors. Specific embodiments can be designed and implemented according to the same principles and specific component compositions.
The thermal media in the thermal media combination may be implemented with different materials and embodiments. Specific materials and embodiments may be air blast, water bath, oil bath, molten low temperature alloy, high temperature salt melt, infrared radiation, microwave radiation, alternating magnetic field, and the like. The operator can flexibly select the materials according to the properties of the materials, the process requirements and other factors. The preferred schemes are blowing, water bath and oil bath. The blowing has the advantages that the settable temperature range is large, the blowing does not contact the surface of the melt, the effect of each angle of the extruded melt is relatively uniform, and the blowing has the defects of low heat transfer efficiency and incapability of quickly realizing temperature control; the water bath has the advantages of high heat transfer speed and easy cleaning of attached water drops; the defects that the settable temperature range is small, and the water flow and other effects have influence on the surface of the wire rod; the oil bath has the advantages of high heat transfer speed, large settable temperature range and capability of meeting the crystallization control requirement of more high polymer materials, and has the defects of more complicated process and unfavorable production management because additional auxiliary equipment is required to remove residual oil on the surface of the wire.
It has also been found in experiments that the residence time of the melt in each section of the heat medium is also an important factor influencing the degree of crystallinity. The specific residence time can be selected and adjusted by factors such as the crystallization rate of the material and the crystallinity requirements for the final product, the extrusion rate, the length of each section of the heat medium, the heat medium material/embodiment, and the like.
It should be understood that the process disclosed in this example is applicable to all polymer extrusion equipment. The particular extrusion equipment may be selected by the operator as appropriate. A common extrusion apparatus comprises: single screw extruders, twin screw extruders, multiple screw extruders, ram extruders, blade plasticating extruders, and the like. Meanwhile, the operator can select additional equipment, such as a melt metering pump, according to actual requirements.
Example 4
The material and the relevant parameters of the crystallization behavior thereof were obtained by extrusion processing of a polycaprolactone material with the CL4580 brand from suzhou polyplex polymer materials ltd, using the detection method of example 1, and by DSC measurement on a DSC-60Plus instrument from shimadzu. The properties of the material related to crystallization behavior were finally measured as follows: t isg＝<Minus 40 ℃; t isc＝39℃；TcoldNone; t ism60.8 ℃. It is seen that the material has only melt crystallization behavior and no cold crystallization behavior.
The embodiment provides a process for controlling the crystallinity of a polymer in an extrusion process, which comprises the following steps:
step S1: melting and extruding the crystalline polymer;
step S2: combining the extruded crystalline polymer melt through a thermal medium to prepare a wire of a polymer material,the heat medium combination comprises 1 section of heat medium and 2 sections of heat medium, wherein the 1 section of heat medium adopts a water bath, and the water temperature T1Wherein T is1At one of 20 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C and 60 deg.C, and has melt shaping and rapid crystallization effects; 2-stage heat medium also adopts water bath with water temperature T2And the temperature is 15 ℃ for wire solidification and shaping.
Comparative example 1
This example provides a process for controlling the crystallinity of a polymer during an extrusion process, which is different from the process for controlling the crystallinity of a polymer during an extrusion process provided in example 1 in that: in step S2, the extruded crystalline polymer melt is passed through only 1 stage of heat medium, and the same 1 stage of heat medium adopts water bath with temperature T1(see Table 1 for specific temperatures).
Comparative example 2
This example provides a process for controlling the crystallinity of a polymer during an extrusion process, which is different from the process for controlling the crystallinity of a polymer during an extrusion process provided in example 1 in that: in step S2, the extruded crystalline polymer melt is passed through only 1 stage of heat medium, and the same 1 stage of heat medium is water bath at 60 ℃.
Comparative example 3
This example provides a process for controlling the crystallinity of a polymer during an extrusion process, which is different from the process for controlling the crystallinity of a polymer during an extrusion process provided in example 4 in that: in step S2, the extruded crystalline polymer melt is passed through only 1 stage of heat medium, and the same 1 stage of heat medium is water bath at 15 ℃.
Experimental example 1 the strands of polymer materials prepared by the process for controlling the crystallinity of a polymer during extrusion process of example 1 and comparative example 1 were evaluated using vicat softening points.
The crystallinity of a wire can be indirectly characterized by measuring the softening point of the wire, with higher softening points representing higher crystallinity of the material. The specific softening point measurement method is as follows: and (3) using an HVT-302B type Vicat softening point tester measured by Shenzhen Wan, taking a small section of wire to be tested, putting the wire into a test platform, pressing a pressing needle at the tip of a load rod to the center of the wire, then immersing the wire into a heat preservation bath, and touching the top end of the load rod by a dial indicator probe. After the pressing pin is positioned for 5min, a weight of 100g is put into the tray at the upper end of the load rod, and the temperature is raised at a constant speed of 120 ℃/h. When the pressing pin is pressed into the sample (1 +/-0.01) mm, the temperature at the moment is quickly recorded, and the temperature is the softening point temperature of the sample. This test example tested the wire softening point data at different temperatures for the polymeric materials prepared using the process for controlling the polymer crystallinity during extrusion processing of example 1 and comparative example 1, and is summarized in table 2 below.
Evaluating the crystallization degree of the L1001 polylactic acid material of Suzhou poly-complex high polymer material Co., Ltd without cold crystallization behavior by adopting a Vicat softening point, wherein the softening point of full crystallization is 145 ℃; and the softening point of the partial crystal is 90-110 ℃; a softening point of <90 ℃ with substantially no crystallization. From table 2, it can be seen from the experimental results of example 1 and comparative example 1 that higher water temperature and oil temperature both contribute to the improvement of the crystallinity of the wire rod. The temperature of the second section of heat medium has a great influence on the crystallinity of the wire, namely, the crystallinity of the wire passes through the 1 section of heat medium with lower temperature and then passes through the 2 sections of heat medium wire with higher temperature is improved.
Table 2: softening point of wire treated at different heat medium temperatures of example 1 and comparative example 1 at a residence time of 120s
*: the softening point temperature is measured under the conditions that the weight is 100g and the heating rate is 120 ℃/h.
Experimental example 2 evaluation of strands of polymer materials prepared by the process for controlling the crystallinity of a polymer during extrusion processing of examples 2 to 3 and comparative example 2.
In the test example, the water tank with adjustable retention time is adopted for verification, and after wires with different retention times are obtained, the Shimadzu DSC-60Plus instrument mentioned in test example 1 is adopted for testing the relative crystallinity of the wires. Detailed description of the inventionThe method comprises the following steps: 50mg of the material to be measured is weighed by a high-precision balance, placed in an aluminum crucible, and then an aluminum upper cover is added, and a sample is pressed and placed in an instrument. The test procedure of the set instrument is as follows: the temperature is raised from room temperature to 230 ℃ at a temperature raising rate of 10 ℃/min, and then the process is finished. From the curve data, the cold crystallization peak (T) was calculatedcoldCorresponding peak) and melting peak (T)mCorresponding peak) area of the sample. The melting peak area can approximately represent the complete crystallization degree of the material, the cold crystallization peak represents the part of the material which is not crystallized yet, and the difference value of the two is the crystallization part formed by the material in the experimental process. Therefore, the relative crystallinity (melting peak area-cold crystallization peak area)/melting peak area corresponds to the experimental data shown in table 3 below.
As can be seen from the data in table 3: (1) from the results of examples 2-3 and comparative example 2, it is found that the process for controlling the crystallinity of the polymer in the extrusion processing process of examples 2-3 can effectively obtain a wire with higher crystallinity by using a two-stage or three-stage heat medium combination compared with the conventional process for controlling the crystallinity of the polymer in comparative example 2 through a low-temperature heat medium; (2) from the comparison of examples 2 and 3, it can be found that the wire rod obtained when the three-stage heat medium was used had higher crystallinity than the wire rod obtained when the two-stage heat medium was used; (3) comparing different data of the wire rod manufactured in example 3, it can be obtained that when three stages of heat media are used, the temperature of the 3 stages of heat media is lower than the glass transition temperature TgWhen the crystallinity of the prepared wire rod is higher than the temperature of the 3-section heat mediumgHigher time; (4) data on the wire obtained in comparative example 3 when T is1、T2And T3Has a temperature relationship of T1<T2，T3<T2Wire ratio T of the obtained wire1<T2<T3The obtained wire has high crystallinity.
TABLE 3 temperature of heat medium and relative crystallinity data for 20s residence time of wire rods prepared in examples 2-3 and comparative example 2
Experimental example 3 evaluation of strands of polymer materials prepared by the process for controlling crystallinity of polymer during extrusion process of example 4 and comparative example 3
In the test example, the water tank with adjustable retention time is adopted for verification, and after the wires with different retention times are obtained, the DSC-60Plus instrument of Shimadzu in test example 1 is adopted to test the relative crystallinity of the wires. The specific test method comprises the following steps: 50mg of the material to be measured is weighed by a high-precision balance, placed in an aluminum crucible, and then an aluminum upper cover is added, and a sample is pressed and placed in an instrument. The test procedure of the set instrument is as follows: heating from-20 deg.C to 150 deg.C at a heating rate of 10 deg.C/min, and finishing. From the curve data, the melting peak (T) was calculatedmCorresponding peak) area of the sample. The melting peak area of the measured wire rod approximately represents the corresponding crystallization degree, and the higher the crystallization degree is, the higher the stability of the wire rod is. The experiment also shows that the retention time of the material in the water bath at 39 ℃ exceeds 30s, the area of the melting peak is not increased any more, and is maintained to be around 48.1J/g. Therefore, the relative crystallinity is defined as melting peak area/maximum melting peak area of the material to be measured, and the corresponding experimental data are shown in table 4 below.
Table 4 data of temperature of heat medium and relative crystallinity for 30s of stay time of wire rods prepared in example 4 and comparative example 3
*: the melt could not be crystallized in the water bath, and remained molten, and no sample could be taken to test the relative crystallinity.
As can be seen from the data in table 4: (1) from the results of example 4 and comparative example 3, it is found that in the extrusion process of example 4, the crystallinity of the polymer is controlled by using the two-stage hot and cold medium combination process, and compared with the traditional process of comparative example 3, the wire with higher crystallinity can be effectively obtained by a low-temperature medium process; (2) when T is used in example 41At different temperatures, T1Is slightly less than TcIn this case, the crystallinity of the wire rod is better.
In summary, the present invention relates to a process for controlling the crystallinity of a polymer during an extrusion process, (1) the heat medium is divided into a plurality of sections, wherein the number of the sections of the heat medium and the specific temperature of each section can be flexibly selected according to the crystallization behavior, chemical properties, cost requirements, etc. of the material, so as to control the thermal history of the material after extrusion, promote the crystallization of the material, and ensure that the extruded product has stable and uniform crystallinity; (2) the material is subjected to online crystallization in a plurality of heat media after being extruded by the process, so that the crystallization of the material is synchronously completed in the extrusion process, no additional post-treatment step is needed, and large draft ratio and complex flow field control are not needed; (3) the process can be widely applied to various crystalline polymers, and has the advantages of low cost, high yield and easy implementation.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A process for controlling the crystallinity of a polymer during extrusion processing, comprising the steps of:
step S1: melting and extruding the crystalline polymer;
step S2: preparing a wire rod of a high polymer material by combining the extruded crystalline high polymer melt through a thermal medium, wherein the thermal medium combination comprises n sections of thermal media, and n is a positive integer; the heat medium through which the melt passes is numbered 1, 2, 3 … n in sequence, and the temperature of the corresponding heat medium is T1，T2，T3…TnThe crystalline polymer shows a cold crystallization behavior, and the glass transition temperature and the cold crystallization temperature of the crystalline polymer are respectively Tg、TcoldThe number n of the sections of the heat medium is more than or equal to 3, and the temperature T of the heat medium1<T2，T3<T2，Tg<T1<Tcold，T3<Tg。
2. The process for controlling the crystallinity of high molecules during extrusion process as claimed in claim 1, wherein the temperature T of the heat medium is determined in step S22And said cold crystallization temperature TcoldThe relationship of (1) is: t iscold–20°C<T2 <Tcold+20°C。
3. The process for controlling the crystallinity of high molecules during extrusion process as claimed in claim 2, wherein the temperature T of the heat medium is determined in step S22And said cold crystallization temperature TcoldThe relationship of (1) is: t iscold–10°C<T2 <Tcold+10°C。
4. The process for controlling the crystallinity of high molecules during extrusion process as claimed in claim 3, wherein the temperature T of the heat medium is determined in step S22And said cold crystallization temperature TcoldThe relationship of (1) is: t iscold–5°C<T2 <Tcold+5°C。
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