TW201309755A - Organically modified layered composite material - Google Patents

Abstract

A organically modified layered composite material the organically modified layered composite and a resin of organically modified layered composite. The organically modified layered composite includes a first material and a second material. The first material is Polyamide, Polyester, Ethylene Vinyl Acetate Copolymer, Ethylene Bis-Stearamide, Magnesium stearate or Zinc stearate. The average of molecular weight of the first material is less than 10, 000. The second material is an organo-modified layered material, and the weight ratio is 1 to 65%. The average space of each layer of the second material is 1 to 9 nm. Therefore, the organically modified layered composite and macromolecule materials will form a good interaction, so as to obtain a preferred mechanical strength, thermal stability, and gas barrier.

Description

Organic modified layered composite

The present invention pertains to a composition of a polymer material, and more particularly to a composition of a polyamine and a polyurethane polymer material resin.

In response to the special needs of products (such as flame resistance, gas barrier properties, etc.), the development and research of many composite materials is continually being carried out. Since the compatibility of polymer materials and inorganic materials in composite materials is poor, inorganic substances must be carried out. The surface is organically modified so that the composite can fully utilize the properties of the inorganic material.

The conventional composite material manufacturing method adds an organically modified layered material to a polymer material, and forms an interaction force between the organically modified layered material and the polymer material, so that the formed composite material obtains a higher molecular material. More good and stable physical and chemical properties (such as mechanical strength, thermal stability, gas barrier, etc.), in order to meet the special needs of the product.

Conventionally, the organically modified layered material is mostly obtained by modifying a cationic surfactant, and is further dispersed in a polymer material by melt-kneading or monomer polymerization with a polymer material. In order to obtain an intercalated or delaminated composite material, the physicochemical properties of the delaminated composite material are preferred.

However, the above-mentioned conventional organically modified layered material still cannot form a good interaction force with most of the polymer materials, and therefore the composite materials formed can only reach the intercalation type and cannot reach the delamination type. Therefore, the composite material obtained by the traditional modification has a very limited improvement in the physical properties.

In view of this, how to develop and improve the shortcomings of the above-mentioned conventional technologies, and to form a good interaction force between the organically modified layered material and the polymer material is a goal that the related industry needs to develop.

In order to solve the above problems, the present invention provides an organically modified layered composite material comprising a first material and a second material. The first material is polyamine or polyester or ethylene-vinyl acetate copolymer or m-ethylbisoctadecylamide or magnesium stearate or zinc stearate, and the first material has an average molecular weight of less than 10,000. The second material is an organically modified layered material, and the weight ratio thereof is 1 to 65% of the organically modified layered composite material, and the average layer spacing of the second material is between 1 and 9 nm.

Therefore, the main object of the present invention is to provide an organically modified layered composite material which forms a good interaction force with a polymer material to obtain better mechanical strength and thermal stability. With gas barrier properties.

In addition, the present invention also provides another polyamide/organomodified layered composite resin comprising a third material and a fourth material, the third material comprising a first material and a second material. The first material is polyamine or polyester or ethylene-vinyl acetate copolymer or m-ethylbisoctadecylamide or magnesium stearate or zinc stearate, and the first material has an average molecular weight of less than 10,000. The second material is an organically modified layered material, and the average layer spacing of each layer of the second material is between 1 and 9 nm. The fourth material is a polyamide or polyamine copolymer.

Therefore, the main object of the present invention is to provide a polyamide/organomodified layered composite material which forms a good interaction force with a polymer material to obtain better mechanical strength. , thermal stability, and gas barrier properties.

In addition, the present invention also provides a polyurethane/organomodified layered composite resin comprising a fifth material and a sixth material, the fifth material comprising the third material and the fourth material, and the third material comprising the first material And the second material. The first material is polyamine or polyester or ethylene-vinyl acetate copolymer or m-ethylbisoctadecylamide or magnesium stearate or zinc stearate, and the first material has an average molecular weight of less than 10,000. The second material is an organically modified layered material, and the average layer spacing of each layer of the second material is between 1 and 9 nm. The fourth material is a polyamide or polyamine copolymer. The sixth material is polyurethane or polyurethaneuride or a copolymer thereof.

Therefore, the main object of the present invention is to provide a polyurethane/organomodified layered composite material which forms a good interaction force with a polymer material to obtain better mechanical strength and heat. Stability, and gas barrier properties.

Since the present invention discloses an organically modified layered composite material, the processes and chemical principles related to the organic materials and polymer materials used therein have been known to those having ordinary knowledge in the related art, and therefore, as explained below, Make a full description. At the same time, the drawings referred to in the following texts express the structural schematics related to the features of the present invention, and do not need to be completely drawn according to the actual size, which is described first.

The present invention provides a first preferred embodiment of an organically modified layered composite material comprising a first material and a second material. The first material may be Polyamide, Polyester, Ethylene Vinyl Acetate Copolymer (EVA), Ethylene Bis-Stearamide (EBS), Magnesium stearate or zinc stearate. The first material has an average molecular weight of less than 10,000 (g/mole). The second material is an organically modified layered material, and the second material accounts for 1 to 65% by weight of the organically modified layered composite material, and the average layer spacing of the second material is between 1 and 9 nm (nm) ).

The organic modified layered composite material provided by the first preferred embodiment comprises the following steps: first, preparing polyamine, polyester, ethylene-vinyl acetate copolymer, ethyl octadecylamide, and hard Magnesium citrate or zinc stearate is used as the first material. The first material is used as a delaminating agent. The average molecular weight of the first material is less than 10,000 as described above, and is preferably from 500 to 10,000.

In addition, the organically modified layered material is prepared as the second material, and the second material of the first preferred embodiment is a modified layered double hydroxides (Modified Layered Double Hydroxides, Modified LDHs). As an organically modified layered material, the second material accounts for 1 to 65% by weight of the total weight of the organically modified layered composite.

The organically modified layered material is added to the organic solvent together with the first material, and after mechanical stirring and grinding, heating is performed to remove the organic solvent. Further, in order to improve the mixing effect of the organically modified layered material and the first material, it is possible to further apply a kneading operation after mechanical stirring and grinding.

However, after the second material provided in the first preferred embodiment, the average layer spacing of each layer is between 1 and 9 nanometers, and the average layer spacing of the second material layer is between 2 and 5 nanometers. optimal. Moreover, the organic modified layered material provided in the first preferred embodiment can be used as a subsequent modified polymeric material.

The experimental examples provided below are based on the use of polyamine as a first material (a delaminating agent).

First experimental example:

Firstly, organic modified clay with an average layer spacing of 1.85 nanometers and polyamine with a molecular weight of 500-10000 were prepared, and the organic modified clay and polyamine were prepared in a ratio of 1:1.

The prepared organic modified clay and polyamine are added to an organic solvent composed of toluene and methanol, mechanically stirred for about 45 to 70 minutes, and ground by a ball mill for about 20 to 35 minutes, with or without kneading. And removing the organic solvent by heating, thereby preparing an organic modified layered composite material.

The organically modified layered composite material obtained through the above steps is an X-ray Diffraction (XRD) method for detecting the average layer spacing of the layers of the organically modified layered material, and at the same time The clay (using commercially available montmorillonite) and the organically modified clay were examined by X-ray diffraction spectrometer as a control.

The average layer spacing value of the organically modified layered material obtained from the 2θ angle of the X-ray diffraction pattern absorption peak of the organic modified layered composite material obtained from the first experimental example of the clay and the organically modified clay composite In Table 1.

As shown in Fig. 1 and Table 1, the clay as a control group had a characteristic absorption peak at a 2θ angle of 8.84 degrees, and the average layer spacing obtained by conversion was 1.00 nm. The X-ray diffraction test in the control group showed that the characteristic absorption peak of the organically modified clay was 4.85 degrees, and the average layer spacing obtained by conversion was 1.85 nm, which was prepared by the first experimental example. The obtained organically modified layered material has a characteristic absorption peak at a 2θ angle of 2.57 degrees, and the average layer spacing obtained by conversion is 3.44 nm.

Therefore, from the above results (Table 1), the organically modified layered composite material provided by the first preferred embodiment of the present invention, wherein the organically modified layered material is compared with the simple clay and the organically modified clay, The average layer spacing is greatly increased.

The present invention further provides a second preferred embodiment which is a polyamide/organomodified layered composite resin. The polyamide/organomodified layered composite resin comprises a third material and a fourth material. The third material is the organic modified layered composite material provided by the first preferred embodiment, wherein the composition selection and material characteristics of the first material and the second material are the same as in the first preferred embodiment. The same is true. The fourth material is a polyamide or a polyamine copolymer, and a polymer material such as Nylon 6 or Nylon 66 is preferred. In the polyamine/organic modified layered composite resin provided in the second preferred embodiment, the weight percentage of the organically modified layered material (second material) is polyamine/organic modified layered composite The average weight of the material resin is from 1 to 30%, and the average layer spacing of each layer of the polyamide/organomodified layered composite resin is from 4 to 6 nm.

The polyamine/organomodified layered composite resin provided by the second preferred embodiment comprises the following steps: First, the organic modified layered composite material is prepared according to the steps provided in the first preferred embodiment. . After the preparation is completed, the obtained organic modified layered composite material is biaxially kneaded with a polyamide or a polyamide polymer to prepare a polyamide/organomodified layered composite resin.

The experimental examples provided below are exemplified by using the organically modified layered composite material provided in the first experimental example as the third material and the Nile 6 polymer material as the fourth material.

Second experimental example:

The organic modified layered composite material was subjected to biaxial mixing operation at a ratio of 10%, 20%, and 50% to a temperature range of 275 ° C to 290 ° C to obtain a Nylon 6 / organic modification. Layered composite resin.

The Nylon 6/organic modified layered composite resin sample of the organic modified clay which was obtained by the foregoing steps and which was 5%, 10%, and 25% by weight of the total composite resin (No. N6, respectively) -MB10, N6-MB20, N6-MB50). The composition of various Nylon 6/organic modified layered composite resins is shown in Table 2 below:

The Nylon 6/organic modified layered composite resin obtained through the above steps is an X-ray diffraction spectrometer for detecting the average layer spacing of the organically modified layered material.

Please also refer to FIG. 2A and Table 3, and FIG. 2A is an X-ray diffraction pattern of the Nylon 6/organic modified layered composite resin sample numbered N6-MB10, N6-MB20, and N6-MB50; The average layer spacing of the organically modified layered material obtained by converting the 2θ angle of the characteristic absorption peak of the sample is shown in Table 3.

The results show that the samples with organic modified clay content of 25%, 10%, and 5% respectively have the characteristic absorption peaks at the angles of 2θ of 1.52 degrees, 1.50 degrees, and 1.49 degrees, respectively, and the organic modified layer is converted. The average layer spacing of the materials is 5.81 nm, 5.89 nm, and 5.93 nm.

2B to 2D are the observations of the Nylon 6/polyamido-organic modified layered composite resin prepared in the second experimental example under transmission electron microscopy (TEM). The magnification is 100,000 times.

As shown by the transmission electron microscopy of the sample No. N6-MB10 shown in Figs. 2A, 2B, and 2C, the average layer spacing of each layer of the organically modified layered material was 4 to 6 nm. 2A, 2B, and 2C, the organic modified layered material (i.e., organically modified clay) of the Nylon 6/organic modified layered composite resin obtained in the second experimental example is uniformly dispersed. In the Nile 6 and the delamination dispersion type.

Therefore, it can be seen from the above that the second preferred embodiment of the present invention can be formed by controlling the molecular weight and weight ratio of the polyamine and the organically modified layered material, respectively. A good interaction force, and can reach the delaminated and dispersed polyamide/organic modified layered composite resin, which can expand the application of the product, strengthen the competitiveness and enhance the commercial value.

The present invention further provides a third preferred embodiment which is a polyurethane/organomodified layered composite resin. The polyurethane/organomodified layered composite resin comprises a fifth material and a sixth material. The fifth material is the polyamine/organomodified layered composite resin provided by the second preferred embodiment, wherein the composition selection and material characteristics of the first material, the second material and the fourth material are The same as described in the first preferred embodiment and the second preferred embodiment. The sixth material is a polyurethane (Polyurethanes), a polyurethane urethane (Polyurethaneurea), or a copolymer of polyurethane and polyurethaneuride.

In the polyurethane/organomodified layered composite resin provided in the third preferred embodiment, the weight percentage of the organically modified layered material is 0.1 to 10 of the total weight of the polyamide/organomodified layered composite. % is preferable, and the average layer spacing of each layer of the organically modified layered material is between 1 and 9 nm, and preferably 2 to 6 nm.

The preparation method is as follows: First, a polyamide/organomodified layered composite resin is prepared according to the steps provided in the first preferred embodiment and the second preferred embodiment. After the preparation is completed, the obtained weight percentage is 1 to 50% (organic modified layered material accounts for the weight ratio of the whole polyamine/organic modified layered composite resin) polyamine/organic modified layered composite The resin of the material and the polyurethane, polyurethaneuride, or the copolymer of polyurethane and polyurethaneurea are subjected to biaxial mixing at a specific temperature, and the polyurethane/organomodified layered composite material is obtained by injection molding. Resin.

The experimental examples provided below are based on the organically modified layered composite material provided in the second experimental example, N6-MB10, N6-MB20, N6-MB50, Nylon 6/organic modified layered composite resin. As a fifth material, and a thermoplastic polyurathane (TPU) is taken as a sixth material.

Third experimental example:

First, 1~50% of the Nylon 6/organic modified layered composite resin and the thermoplastic polyurethane are stirred and mixed at a specific temperature, and subjected to biaxial mixing operation to obtain the final organic by injection molding. The modified clay accounts for 1%, 2%, 5% of the total composite resin TPU/Nanlun 6/organic modified layered composite resin (No. UN6-FR-2, UN6-FR-3, UN6- FR-4). Further, a thermoplastic polyurethane was prepared in a ratio of 80% and 20% by weight to a control sample of UN6-FR-1 at a ratio of 80% to 20% by weight. The composition of each sample is shown in Table 5 below:

The TPU/Nanlun 6/organomodified layered composite resin obtained through the above steps is an X-ray diffraction spectrometer for detecting the average layer spacing of the organically modified layered material.

Please also refer to Figure 3 and Table 6. Figure 3 shows the sample of TPU/Nanlun 6/organic modified layered composite resin sample numbered UN6-FR-2, UN6-FR-3, and UN6-FR-4. - The light diffraction pattern; and the average layer spacing value of the organically modified layered material obtained by converting the 2θ angle of the characteristic absorption peak of each sample is shown in Table 6.

The TPU/Nanlun 6/organic modified layered composite material was observed by X-ray diffraction spectrometer. The sample obtained in the third experimental example and the Nylon 6/organic modified layered composite material in the second experimental example, The same is evenly dispersed, and the layer spacing is greatly increased. Please also refer to Figure 3 and Table 6. For samples with organic modified clay content of 1%, 2%, and 5%, the 2θ angles of the characteristic absorption peaks are 1.49 degrees, 1.50 degrees, and 1.52 degrees, respectively. The average layer spacing of the organically modified layered materials is 5.81 nm, 5.89 nm, and 5.93 nm, respectively.

The above description is only the preferred embodiment of the present invention, and is not intended to limit the patent application rights of the present invention. The above description should be understood and implemented by those skilled in the art, so that the other embodiments are not deviated from the present invention. Equivalent changes or modifications made in the spirit of the disclosure should be included in the scope of the patent application.

Fig. 1 is a graph showing experimental results of an organic modified layered composite material analyzed by an X-ray diffraction spectrometer according to a first experimental example of the present invention.

2A is a graph showing experimental results of analysis of a Nylon 6/organic modified layered composite resin according to a second experimental example of the present invention by an X-ray diffraction spectrometer.

2B is a transmission electron micrograph of the numbered N6-MB10 sample of the second experimental example of the present invention.

2C is a transmission electron micrograph of the numbered N6-MB20 sample of the second experimental example of the present invention.

2D is a transmission electron micrograph of the numbered N6-MB50 sample of the second experimental example of the present invention.

3 is a graph showing experimental results of a TPU/Nanlun 6/organic modified layered composite material subjected to an X-ray diffraction spectrometer according to a third experimental example of the present invention.

Claims (10)

An organically modified layered composite material comprising a first material and a second material, wherein the first material is selected from the group consisting of polyamine, polyester, ethylene-vinyl acetate copolymer, and ethyl a group consisting of bis-octadecyl amide, magnesium stearate, and zinc stearate, and the first material has an average molecular weight of less than 10,000; and the second material is an organically modified layered material The weight percentage is 1 to 65% of the organic modified layered composite material, and the average layer spacing of each layer of the second material is between 1 and 9 nm. The organically modified layered composite material according to claim 1, wherein the second material is clay or hydrotalcite. The organically modified layered composite material according to claim 1, wherein the average spacing of the layers of the second material is between 2 and 5 nm. A polyamine/organic modified layered composite resin comprising a third material and a fourth material, wherein the third material comprises a first material and a second material, wherein the first material is a group selected from the group consisting of polyamine, polyester, ethylene-vinyl acetate copolymer, ethyl bis-octadecylamide, magnesium stearate, and zinc stearate, and the average molecular weight of the first material Is less than 10000; the second material is an organically modified layered material, and the average spacing of the layers of the second material is between 1 and 9 nm; and the fourth material is selected from the group consisting of polyamine and polyamine A group of copolymers. The polyamide/organomodified layered composite resin according to claim 4, wherein the weight percentage of the organic modified layered material is 1 of the polyamine/organic modified layered composite resin ~30%. The polyamide/organomodified layered composite resin according to claim 4, wherein the fourth material is Nylon 6 or Nylon 66. The polyamide/organomodified layered composite resin according to claim 4, wherein the average layer spacing of each layer of the organically modified layered material is between 4 and 6 nm. A polyurethane/organomodified layered composite resin comprising a fifth material and a sixth material, wherein the fifth material comprises a third material and a fourth material, and the third material comprises a first a material and a second material, wherein the first material is selected from the group consisting of polyamine, polyester, ethylene-vinyl acetate copolymer, ethylidene octadecylamide, magnesium stearate, and zinc stearate a group of the first material having an average molecular weight of less than 10,000; the second material is an organically modified layered material, and the average layer spacing of the second material is between 1 and 9 nm; The four materials are selected from the group consisting of polyamines and polyamine copolymers; and the sixth material is selected from the group consisting of polyurethanes, polyurethaneureas, and copolymers thereof. The polyurethane/organomodified layered composite resin according to claim 8, wherein the weight ratio of the organically modified layered material is 0.1 to 10% of the polyurethane/organomodified layered composite resin. The polyurethane/organomodified layered composite resin according to claim 8, wherein the organic layered material has an average layer spacing of 4 to 6 nm.