TW201930398A - Foam material and fabricating method thereof - Google Patents

Abstract

A foam material and a fabricating method thereof are provided. The form material is formed by a polymer material including a polyamide 6 and a copolyamide. The polymer material has two melting point above 180 DEG C. The structural unit constituting the copolyamide includes a structural unit derived from caprolactam. The polyamide co-polymer has a melting point of 160 DEG C to 200 DEG C.

Description

Foaming material and method of manufacturing same

The present invention relates to a foamed material and a method of manufacturing the same, and more particularly to a high temperature resistant foamed material and a method of producing the same.

The polymer foaming material is widely used in the fields of people's livelihood, biomedicine, optoelectronics, energy, and aerospace materials because of its light weight, excellent thermal insulation properties, impact resistance and sound insulation. Among polymer foam materials, bead foam (or expandable foam) is easy to manufacture low-density foamed blocks of various shapes and high precision. In recent years, more and more attention has been paid.

Commercially available bead materials include expandable polystyrene (EPS), expandable polyethylene (EPE), expandable polypropylene (EPP), and expandable thermoplastic polyurethane. (expandable thermoplastic polyurethane, ETPU) and expandable polylactic acid (EPLA) and other materials. However, the above-mentioned bead material cannot be used for a long time at a high temperature of 150 °C. In addition, the expandable polystyrene may release residual styrene monomer at a high temperature, and the disadvantages of swelling after moisture, high moisture permeability, and poor solvent resistance also limit its applicability. Expandable polypropylene has the disadvantage of being melt strength and costly. Expandable thermoplastic polyurethanes also have the disadvantage of being less rigid and less prone to making low density foamed materials.

On the other hand, heat-resistant polymer materials such as polyamides have excellent mechanical properties, heat resistance, and good abrasion performance, but are not easy due to crystallinity and relatively high process temperature. Foaming forms a foamed material.

Based on the above, how to develop a high temperature resistant bead material is an important subject for research in the industry.

The invention provides an expandable foaming material (bubble material), in particular to a high temperature resistant foaming material containing polyamidamine as a main component and a manufacturing method thereof, and solves the problem that the polyamide is crystalline and high in the past. The process temperature is not easy to foam.

The present invention provides a foamed material which is formed of a polymer material including polyamine 6 and copolymerized decylamine, and the polymer material has two melting points of 180 ° C or higher. The structural unit constituting the copolymerized decylamine includes a structural unit derived from caprolactam having a melting point of 160 ° C to 200 ° C.

In one embodiment of the present invention, the above polyamine 6 has a melt index of from 15 g/10 min to 60 g/10 min under the conditions of ASTM D1238 and a load of 5 kg at 275 °C.

In one embodiment of the present invention, the above copolymerized decylamine has a melt index of from 20 g/10 min to 40 g/10 min under the conditions of ASTM D1238 and a load of 5 kg at 275 °C.

In an embodiment of the invention, the difference between the first melting point and the second melting point of the polymer material is 9 ° C or higher.

In an embodiment of the invention, the first melting point of the polymer material ranges from 190 ° C to 215 ° C, and the second melting point ranges from 205 ° C to 220 ° C, wherein the second melting point is higher than the first melting point.

In an embodiment of the present invention, the total amount of the polymer material is 100% by weight based on the polyamidoamine 6 and the copolymerized decylamine, and 10 to 80% by weight of the polyamidoamine 6 is copolymerized with decylamine. 20% by weight to 90% by weight.

The present invention also provides a method of producing a foamed material, which comprises the following steps in sequence. First, polyamine 6 is mixed with a copolymerized decylamine to form a polymer material. Next, the first foaming step is performed. Specifically, the polymer material is impregnated with carbon dioxide at a pressure of 6.9 MPa to 30 MPa and a temperature of 80 ° C to 120 ° C to obtain a carbon dioxide-saturated foamed material. Then, the carbon dioxide-saturated foamed material is released to atmospheric pressure. Next, a second foaming step is performed. Specifically, the carbon dioxide-saturated foamed material is heated to form a semi-finished product of the foamed material. The semi-finished product of the foamed material is then cooled to form a foamed material. The foamed material has two melting points above 180 °C.

In an embodiment of the invention, in the first foaming step, the pressure of the impregnated polymer material is from 10 MPa to 15 MPa.

In an embodiment of the present invention, in the second foaming step, the foamed material saturated with carbon dioxide is placed in a high temperature oil bath of 180 ° C to 220 ° C.

In an embodiment of the invention, in the second foaming step, the time during which the carbon dioxide-saturated foamed material is heated is from 1 second to 300 seconds.

Based on the above, the present invention provides a foamed material and a method for producing the same, which comprises using a polymer comprising polyamine 6 and a copolymerized decylamine and having two melting points of 180 ° C or higher (ie, double melting peaks). Materials to prepare high temperature resistant foamed materials.

The above described features and advantages of the invention will be apparent from the following description.

The invention provides a foam material by using a polymer material, wherein the polymer material comprises polyamine 6 and copolymerized decylamine. Polyamine 6 and copolyamine are those having a repeating unit of a guanamine bond (-CONH-), a ring-opening polymerization via (1) an indoleamine, (2) polycondensation of an aminocarboxylic acid, and (3) binary A polymer prepared by a polymerization method such as polycondensation of an amine and a dibasic acid. Polyammonium 6 and copolyamine are preferably crystalline polymers.

Polyamine 6 may have a melting point of from 220 ° C to 225 ° C. Polyamide 6 may have a crystallization point temperature of from 175 ° C to 185 ° C. The polyamine 6 may have a crystallinity of 10% to 20%, preferably 13.0% to 19.0%. Further, the melt index of the polyamide 6 may be 15 g/10 min to 60 g/10 min under the conditions of ASTM D1238 and a load of 5 kg at 275 °C.

The polyamine 6 may be from 10% by weight to 80% by weight, preferably from 20% by weight to 50% by weight, more preferably from 20% by weight to 30%, based on 100% by weight of the polyamine 6 and the copolymerized decylamine. weight%. When the content of the polyamide 6 is in the above range, the difference between the first melting point described below and the second melting point described below is large, and the processing temperature is widened, which contributes to an increase in workability of the foamed material.

Copolyamine is a copolymer modified with polyamine 6 as a main component. Further, the structural unit constituting the copolymerized decylamine includes a structural unit derived from caprolactam (CPL) as a monomer. The copolyamine may have a melting point of from 160 ° C to 200 ° C, preferably from 170 ° C to 195 ° C, more preferably from 170 ° C to 180 ° C. If the melting point is less than 160 ° C, the difference in melt viscosity between the copolymerized decylamine and the polyamide 6 is too large, and the polymer is kneaded unevenly; if the melting point is greater than 200 ° C, the first melting point and the second melting point of the polymer material are obtained. The difference between the two is too small, resulting in insufficient processing temperature of the foamed material, which is unfavorable for application.

The other structural unit constituting the copolymerized decylamine is not particularly limited as long as the melting point of the copolymerized decylamine is within the above range. Specifically, the monomers constituting the other structural unit may be selected from the group consisting of copolymerized decylamine 6/66, copolymerized decylamine 6/6, 10, copolymerized decylamine 6/6, 12, copolymerized decylamine 6/6T, and copolymerized decylamine 6/. 6I, copolyamine 6/66/6I, copolyamine 6/66/6T, polyamine 6/6, 10/6T, polyamine 6/6, 10/6I, copolyamine 6/6,12 /6T and the monomers used in the copolymerization of decylamine 6/6, 12/6I. In detail, examples of the monomer constituting the other structural unit include monomers such as hexamethylenediamine, adipic acid, sebacic acid, ω-aminododecanamide, terephthalic acid, and isophthalic acid. The crystallization point temperature of the copolyamine can be from 135 ° C to 140 ° C. The copolymerization of the decylamine may be from 10% to 15%, preferably from 11.0% to 13.0%. Further, based on ASTM D1238 and at a load of 5 kg at 275 ° C, the copolymerization of the decylamine may be from 20 g/10 min to 40 g/10 min.

The copolymerized guanamine may be from 20% by weight to 90% by weight, preferably from 50% by weight to 80% by weight, more preferably from 70% by weight to 80% by weight based on 100% by weight of the total of the polyamine 6 and the copolymerized decylamine. %. When the content of the copolymerized decylamine is in the above range, the difference between the first melting point described below and the second melting point described below is large, and the range of the processing temperature is wide, which contributes to an increase in workability of the foamed material.

From the viewpoint of high temperature resistance, the polymer material preferably has two melting points of 180 ° C or higher, more preferably two melting points of 190 ° C or higher, and even more preferably between two 190 ° C and 250 ° C. Melting point. Specifically, the foamed material usually has two or more melting point peaks to serve as a bead material. In the present invention, the sample is heated at a fixed rate of temperature rise, and the endothermic peak appearing for the first time in the differential scanning calorimetry curve is defined as the first melting point, and the second endothermic peak is defined as the second melting point.

In subsequent processes, the processing temperature of the foamed material must range between the first melting point and the second melting point. When the ambient temperature at which the foamed material is placed is between the first melting point and the second melting point, a portion of the polymer having a melting point of the first melting point is melted, and the foamed material can be used as a molten bonding material. Further, in the foamed material, the entire structure of the polymer-supported foamed material having a melting point of the second melting point which is not melted is still present, so that the foamed material is not deformed.

The greater the difference between the first melting point and the second melting point, the better the extent of the processable temperature range (i.e., processability). Specifically, the difference between the first melting point and the second melting point may be 9 ° C or higher, preferably 12 ° C or higher (that is, workability). Additionally, the first melting point can range from 190 °C to 215 °C. The second melting point may range from 205 ° C to 220 ° C, wherein the second melting point is higher than the first melting point. When the first melting point is lower and/or the second melting point is higher, the difference between the first melting point and the second melting point is larger, and the processing temperature is wider, which helps to increase the processability of the foamed material. Further, when the first melting point is too high, for example, more than 250 ° C, there is a disadvantage that the temperature required for processing is too high and processing is difficult.

The polymer material of the present invention may further include additives such as a reinforcing filler, an organic decane-based compound flame retardant, an impact modifier, other polymers, or a processing aid. The processing aid is selected from one or more of an antioxidant, a heat resistant stabilizer, a weathering agent, a mold release agent, a lubricant, a pigment, a dye, a plasticizer, and an antistatic agent.

The foamed material of the present invention may have a density of from 0.03 g/cm ³ to 0.5 g/cm ^{3 ,} preferably from 0.2 g/cm ³ to 0.3 g/cm ³ . When the density is low, it is beneficial for applications such as thermal insulation, impact resistance and sound insulation. The application of the foamed material is lightweight and material saving, and the density of the foamed material can be adjusted according to different applications. If the density of the foamed material is too high, the material cannot be saved, and if the density of the foamed material is too low, the material properties and mechanical properties of the material are significantly affected. When the density of the foamed material is less than 0.03, the heat transfer coefficient is increased, resulting in failure to insulate.

The expansion ratio of the foamed material of the present invention may preferably be 3.5 or more. When the expansion ratio is high, it is advantageous for applications such as heat insulation, impact resistance and sound insulation.

The foamed material of the present invention can be produced by a batch foaming method or a continuous underwater water pelletization. From the viewpoint of commercialization, it is preferred to produce a foamed material by a water granulation method.

The batch foaming method as a foaming material manufacturing method sequentially includes the following steps:

(1) Step of forming a polymer material: Polyamine 6 and a copolymerized decylamine are mixed at a desired fixed ratio to form a polymer material, and for example, polyamine 6 and a copolymerized decylamine are kneaded by a kneader.

(2) First foaming step: the polymer material is first placed in a high pressure bath, and the polymer material is in carbon dioxide at a pressure of, for example, 6.9 MPa to 30 MPa and a temperature of 80 ° C to 120 ° C. Immersion to obtain a foamed material saturated with carbon dioxide. The desired cell size is achieved by controlling the pressure and temperature at which the polymer material is impregnated. The pressure at which the polymer material is impregnated in carbon dioxide can be adjusted in accordance with the saturation temperature of the polymer material itself. The temperature at which the polymer material is impregnated in carbon dioxide is set to 80 ° C to 120 ° C, and the expansion ratio of the foamed material is high. When the temperature at which the polymer material is impregnated in carbon dioxide is set to less than 80 ° C, the prepared foamed material exhibits a solid-like state, and the foaming result is not good.

In the above process of impregnating the polymer material, carbon dioxide is absorbed into the interior of the polymer material to be saturated, and the time for impregnating the polymer material may be 5 to 48 hours, preferably 5 to 24 hours.

(3) Pressure relief step: The carbon dioxide-saturated foaming material is depressurized to atmospheric pressure, for example, the carbon dioxide-saturated polymer material is released to atmospheric pressure and then taken out from the high pressure tank.

(4) Second foaming step: heating the carbon dioxide-saturated foamed material to form a semi-finished product of the foamed material. In detail, when the temperature is heated to a glass transition temperature higher than that of the carbon dioxide-saturated polymer material, the polymer material undergoes nucleation and cell growth, which in turn causes foaming. A general heating device can be used to heat the carbon dioxide-saturated polymer material. For example, a hot water bath, an oil bath, a hot air, a vapor, a radiation, a heating plate, or the like can be used to heat the carbon dioxide-saturated polymer material. The second foaming step is carried out, for example, by placing a carbon dioxide-saturated foamed material in a high-temperature oil bath of 180 ° C to 220 ° C for 1 second to 300 seconds.

(5) Cooling step: The semi-finished product of the foamed material is rapidly cooled to fix the cell structure in the foamed material. For example, the semi-finished product of the foamed material formed after heating can be rapidly cooled by being placed in an ice water bath.

The invention is further described in the following examples, but it should be understood that these examples are merely illustrative and are not to be construed as limiting. < Evaluation method >

The evaluation methods in the synthesis examples and the examples are as follows. a. Measurement of melting point temperature (T _m ), crystallization point temperature (T _c ) and crystallinity (X _c ) of polymer materials

About 5 mg of the polymer material after the kneading was measured and measured by differential scanning calorimetry (DSC). Specifically, a differential scanning calorimeter (Model DSC 4000, manufactured by PerkinElmer Co., Ltd.) was used, and the test conditions were from 30 ° C to 280 ° at a heating rate of 10 ° C / min under a nitrogen atmosphere. C (first heating), then from 280 ° C to 30 ° C at a cooling rate of 10 ° C / min, and finally from 30 ° C to 280 ° C at a heating rate of 10 ° C / min (second heating) The differential scanning calorimetry curve (DSC curve) was observed, and the melting point temperature (T _m ), the crystallization point temperature (T _c ), and the calculated crystallinity (X _c ) were obtained.

The calculation of the crystallinity calculation is as follows. Assuming that the polyamine 6, ₁₀₀ % crystalline theoretical heat of fusion rH _100% is 230 J / g, take the point where the baseline horizontal line in the differential scanning calorimetry curve starts to shift as the starting point after taking the double melting point The baseline trend level is the end point, and the area surrounded by the curve and the reference line can be used to obtain the melting heat rH. The ratio of the melting heat rH to the 100% crystal melting heat rH _100% is the crystallinity. In the case of a foamed material, the crystal portion cannot be foamed, so that the material having a higher crystallinity is more difficult to foam. b. Observation of foaming materials

The foamed material was placed in liquid nitrogen for 5 minutes and quickly brittle with a diagonal pliers. Next, the foamed material after the brittle fracture is adhered to the stage using carbon glue. Then, the foam material and the stage are placed in a gold plating machine (Model JFC-1300) with gold plating. Thereafter, the stage on which the foamed material was placed was placed in a scanning electron microscope (Model JSM-6390LV, manufactured by JT Co., Ltd.) to observe and photograph the form of the foamed material. c. Measurement of the density of foamed materials

The weight of the foamed material in the air and the weight in the water were measured using a microbalance (Tc), and the density of the foamed material was calculated by the following formula (1). Formula (1) ρ _f : density of foamed material (g/cm ³ ) W _{in air} : weight of foamed material in air (g) W _{in water} : weight of foamed material in water (g) ρ _{H 2 O} : density of water (g/cm ³ ) d. measurement of expansion ratio

The expansion ratio is a ratio of the solid density of the polymer material itself to the density of the above-mentioned foamed material. < Synthesis Example >

Hereinafter, Synthesis Example 1 to Synthesis Example 6 of the polymer material will be described:

The polyamine 6 and the copolymerized decylamine used in the synthesis examples are as described in Table 1 below. 2A to 2C are differential scanning calorimetry curves of polyamine 6 and copolyamide used, respectively.

Table 1 [Synthesis Example 1]

The polyamine 6 and the copolymerized decylamine were respectively dried in an oven at 80 ° C for 16 hours to remove water. Next, a sample of 20% by weight of polyamidamine 6 and 20% by weight of copolyamine was placed in a micro-kneader (Model MC-15, Xplore Technology) for 1 minute. To prepare a polymer material. The gas atmosphere of the mixer was nitrogen, and the three temperatures were set to 230 ° C, 250 ° C and 250 ° C, respectively, and the rotation speed was 50 rpm. Finally, the polymer material of Synthesis Example 1 was obtained. [Synthesis Examples 2 to 6]

The polymer materials of Synthesis Examples 2 to 6 were prepared in the same manner as in Synthesis Example 1, and were distinguished by changing the kind and ratio of the polyamide 6 and the copolymerization oxime. (As shown in table 2).

Table 2 < Example >

Examples 1 to 6 and Comparative Examples 1 and 2 of the foamed material are described below: [Example 1] a. Preparation of foamed material

0.1 g of the polymer material of Synthesis Example 1 was placed in an oven at 80 ° C for 16 hours to remove moisture. Next, the sample was placed in a high pressure bath and carbon dioxide was introduced therein, wherein the impregnation pressure was 13.8 MPa, the impregnation temperature was 80 ° C, and the impregnation temperature was 24 hours. Then, the carbon dioxide-saturated polymer material is released to atmospheric pressure and then taken out from the high pressure tank. Next, the carbon dioxide-saturated polymer material was placed in a high-temperature oil bath at 200 ° C for 3 minutes to form a semi-finished product of the foamed material. Finally, the semi-finished product of the foamed material is rapidly cooled in an ice water bath to obtain a foamed material (as shown in Fig. 1A). b. Foaming material bonding test

In the preparation of the a. foaming material described above, after the polymer material is impregnated with carbon dioxide, the carbon dioxide-saturated polymer material is then placed in a high-temperature oil bath at 213 ° C for 3 minutes to carry out the second foaming. Then, the temperature of the high temperature oil bath was raised to 215 ° C to bond between the foamed material particles to form a bonded foamed material (as shown in FIG. 1B ). [Examples 2 to 3 and Comparative Example 1]

Examples 2 to 3 and Comparative Example 1 were prepared in the same manner as in Example 1 except that the polymer material of Synthesis Example 1 was used in the same manner as in Example 1, and the difference was that the impregnation temperature was changed (as shown in Table 3). . [Examples 4 to 6 and Comparative Example 2]

The foaming materials of Examples 4 to 6 and Comparative Example 2 were prepared in the same manner as in Example 1, and were different in that the polymer material of Synthesis Example 1 was replaced with the polymer material of Synthesis Example 4, and was changed. Impregnation temperature (as shown in Table 3).

table 3 < evaluation result >

Table 2 shows the first melting point temperature (T _{m (low)} ) and the second melting point temperature (T _{m (low)} ) of the synthesis examples 1 to 6 under the change of the type and ratio of the polyamide 6 and the copolymerization enthalpy, and the first The difference between the melting point temperature and the second melting point temperature (ΔT _m , hereinafter referred to as "melting point difference"), the crystallization point temperature (T _c ), and the crystallinity (X _c ). 3A to 3F are differential scanning calorimetry measurement curves (DSC curves) of the polymer materials of Synthesis Examples 1 to 6. According to Table 2, FIG. 3A to FIG. 3F, the polymer materials of Synthesis Examples 1 to 6 all have two melting points of 180 ° C or more and have a melting point difference of 9 ° C or more, and thus can be used as a foaming material and have a foaming material. Processability. Further, Synthesis Examples 1 and 3 had larger melting point differences than Synthesis Example 2, and Synthesis Examples 4 and 6 had larger melting point differences than Synthesis Example 5. It can be seen that when the weight ratio (wt%) of the polyamidamine 6 to the copolymerized decylamine is from 20:80 to 50:50, the polymer material has a large difference in melting point, so that the formed foamed material has better Processability.

Table 3 shows the types and ratios of the polymer materials used in Examples 1 to 6 and Comparative Examples 1 and 2, and the density and expansion ratio of the foamed material. According to Table 3, when the impregnation temperature was 80 ° C or more (Examples 1 to 3 and Examples 4 to 6), the foamed material exhibited nearly four times the expansion ratio. On the other hand, when the impregnation temperature was less than 80 ° C (Comparative Examples 1 and 2), the expansion ratio of the foamed material was low, and the foamed material exhibited a solid-like state, and the foaming result was poor.

4A to 4C are SEM images of cross sections of the foamed materials of Examples 1 to 3. 5A to 5C are SEM images of cross sections of the foamed materials of Examples 4 to 6. 4A to 4C and 5A to 5C, the foamed materials of Examples 1 to 6 exhibited good foaming properties.

On the other hand, in the foaming materials of Comparative Examples 1 and 2, the foaming property was not foamed, and therefore the foaming property was poor.

In summary, the present invention uses a polymer material having two melting points (double melting peaks) of 180 ° C or higher to prepare a high temperature resistant foaming material, and the foaming material has good processability by passing through a double melting peak.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

no

Fig. 1A is a photograph of the foamed material of Example 1. 1B is a photograph of the bonded foamed material of Example 1. 2A is a differential scanning calorimetry curve of polyamido 6 (first sample). 2B is a differential scanning calorimetry curve of polyamido 6 (second sample). Figure 2C is a differential scanning calorimetry curve of copolyamide. 3A to 3F are graphs showing the differential scanning calorimetry of the polymer materials of Synthesis Examples 1 to 6. 4A to 4C are SEM images of cross sections of the foamed materials of Examples 1 to 3. 5A to 5C are SEM images of cross sections of the foamed materials of Examples 4 to 6.

Claims (10)

A foaming material formed of a polymer material comprising polyamine 6 and a copolymerized decylamine, and the polymer material having two melting points of 180 ° C or higher to constitute the copolymerized decylamine The structural unit includes a structural unit derived from caprolactam having a melting point of 160 ° C to 200 ° C. The foaming material according to claim 1, wherein the polyamide® has a melt index of 15 g/10 min to 60 g based on ASTM D1238 and a load of 5 kg at 275 ° C. 10 minutes. The foaming material according to claim 1, wherein the copolymerized decylamine has a melt index of from 20 g/10 min to 40 g/10 based on ASTM D1238 and at a load of 5 kg at 275 ° C. minute. The foamed material according to claim 1, wherein a difference between the first melting point and the second melting point of the polymer material is 9 ° C or more. The foaming material according to claim 1, wherein the first melting point of the polymer material ranges from 190 ° C to 215 ° C, and the second melting point ranges from 205 ° C to 220 ° C, wherein the second melting point is high. At the first melting point. The foaming material according to claim 1, wherein in the polymer material, the polyamine 6 is based on 100% by weight of the total of the polyamide and the copolymerized decylamine. The copolyamide is from 20% by weight to 90% by weight, based on 10% by weight to 80% by weight. A method for producing a foamed material, comprising: mixing polyamine 6 with a copolymerized decylamine to form a polymer material; first foaming step at a pressure of 6.9 MPa to 30 MPa and 80 ° C to 120 ° C At a temperature, the polymer material is impregnated in carbon dioxide to obtain a carbon dioxide-saturated foaming material; the carbon dioxide-saturated foaming material is depressurized to atmospheric pressure; and a second foaming step is performed to heat the carbon dioxide The foamed material is saturated to form a semi-finished product of the foamed material, and the semi-finished product of the foamed material is cooled to form a foamed material, wherein the foamed material has two melting points of 180 ° C or more. The method for producing a foamed material according to claim 7, wherein in the first foaming step, the pressure of impregnating the polymer material is from 10 MPa to 15 MPa. The method for producing a foamed material according to claim 7, wherein in the second foaming step, the carbon dioxide-saturated foamed material is placed in a high-temperature oil tank of 180 ° C to 220 ° C. get on. The method for producing a foamed material according to claim 7, wherein in the second foaming step, the carbon dioxide-saturated foamed material is heated for a time of from 1 second to 300 seconds.