CN115895040B - Modified layered nano material and application thereof in preparation of PPR material - Google Patents
Modified layered nano material and application thereof in preparation of PPR material Download PDFInfo
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Abstract
The invention provides a modified layered nano material and application thereof in preparing a PPR material. The modified layered nano material is obtained by ball milling a layered nano material and a modifier, wherein the modifier is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, titanate coupling agent 201 and titanate coupling agent 311. When the modified layered nano material is used for modifying the PPR material, the cold material spots and trace areas formed on the surfaces of the inner wall and the outer wall of the PPR material in the extrusion process can be reduced, so that the cold material spots and trace areas cannot be observed by naked eyes, the migration of bubbles to the surface can be prevented, the radius of the bubbles is reduced, the formation of bubbles visible to naked eyes is inhibited, and the number of bubbles on the surfaces of the inner wall and the outer wall of the PPR material is reduced, so that the modified layered nano material can effectively improve the mechanical property and the surface quality percent of pass of the PPR material.
Description
Technical Field
The invention belongs to the technical field of material modification. More particularly, it relates to a modified layered nanomaterial and its application in preparing PPR material.
Background
Random copolymer polypropylene (pentatricopeptide repeats, PPR) is obtained by random copolymerization of propylene with a small amount of comonomers (mainly ethylene, sometimes 1-butene and 1-hexene) at a certain temperature and pressure and with the aid of a catalyst. The PPR structure has the performance which is not possessed by homo-polypropylene (PP-H) and block-copolymerized polypropylene (PPB), becomes a novel polypropylene material, and is widely applied to the fields requiring transparency, low melting point and high temperature pressure resistance, such as films for clothing and food packaging, transparent containers for daily necessities and food storage, medical appliances, heat-sealing orientation films, pressure-resistant pipes and the like.
At present, the PPR material is mainly produced by adopting an extrusion-hot stretching-quenching method, but cold material spots, marks, bubbles and the like are easy to appear on the surfaces of the inner wall and the outer wall of the PPR material produced by the method, so that the quality percent of pass of the surface of the PPR material is reduced, and the mechanical property is reduced. In order to solve the problem, the prior art generally modifies the random copolymer polypropylene, such as the prior art adopts a grafted polyolefin-based montmorillonite master batch as a modified material of the random copolymer polypropylene, but the modified material needs to mix the organic montmorillonite containing alkyl quaternary ammonium salt or the purified montmorillonite with an epoxy compound, and then the modified material is subjected to strong shearing and mixing at high temperature (150-200 ℃), and then the grafted polyolefin-based modified material is obtained, so that the process is complex, the condition is harsh, and the mass production is not facilitated.
Therefore, a need exists for a modified material which is simple to prepare and can effectively improve the mechanical property and the surface quality qualification rate of PPR materials, and has quite necessity for application of PPR materials in the aspects of films, containers, pipes and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a modified layered nano material which is simple to prepare, and when the modified layered nano material is used for modifying a PPR material, the generation of cold material spots, trace marks and bubbles on the inner wall and the outer wall of the PPR material is effectively reduced, so that the mechanical property and the surface quality qualification rate of the PPR material are effectively improved.
The invention also aims to provide the application of the modified layered nano material in preparing PPR materials.
It is another object of the present invention to provide a high surface quality PPR material.
It is a further object of the present invention to provide a method for preparing a high surface quality PPR material.
It is a further object of the present invention to provide the use of the above-mentioned high surface quality PPR material for the preparation of films, containers and/or pipes.
The above object of the present invention is achieved by the following technical scheme:
the invention provides a modified layered nano material, which is obtained by ball milling a layered nano material and a modifier, wherein the modifier is one or more of Cetyl Trimethyl Ammonium Bromide (CTAB), sodium Dodecyl Sulfate (SDS), a titanate coupling agent 201 and a titanate coupling agent 311.
When the modified layered nano material is used for modifying a PPR material, the modified layered nano material is well compatible with the PPR material, can successfully fill in molecular gaps of the PPR material to form a layered blocking structure, can reduce cold material spots and trace areas formed on the surfaces of the inner wall and the outer wall of the PPR material in the extrusion process, can not be observed by naked eyes, can also prevent bubbles from migrating to the surface, can reduce the radius of the bubbles, can inhibit the formation of bubbles visible by naked eyes, and can reduce the number of bubbles on the surfaces of the inner wall and the outer wall of the PPR material, so that the modified layered nano material can effectively improve the mechanical property and the surface quality qualification rate of the PPR material.
Preferably, the layered nanomaterial is a two-dimensional layered nanomaterial.
Further preferably, the two-dimensional layered nanomaterial is montmorillonite (MMT) and/or Hydrotalcite (HT).
More preferably, when the two-dimensional layered nanomaterial is montmorillonite (MMT), the modifier is one or more of cetyltrimethylammonium bromide (CTAB), sodium Dodecyl Sulfate (SDS), and titanate coupling agent 201; when the two-dimensional layered nanomaterial is Hydrotalcite (HT), the modifier is one or more of Cetyl Trimethyl Ammonium Bromide (CTAB), sodium Dodecyl Sulfate (SDS) and titanate coupling agent 311.
Preferably, the mass ratio of the layered nano material to the modifier is 3-5: 0.1 to 0.5.
Preferably, the ball milling is dry ball milling and/or wet ball milling.
Preferably, the ball milling is performed at 400-500 rpm for 8-24 hours. The ball milling process is simple, has short time consumption, can obviously reduce energy consumption, is green and environment-friendly, and meets the actual production requirements, the ball milling condition can obviously reduce the surface energy and the hydrophilic performance of the layered nano material, the uniform dispersion degree of the layered nano material is improved, and the modified layered nano material is endowed with strong hydrophobicity and high dispersibility.
The modified layered nano material can effectively improve the mechanical property and the surface quality qualification rate of the PPR material, so that the application of the modified layered nano material in preparing the PPR material is within the protection scope of the invention.
The invention also provides a high-surface-quality PPR material, which comprises the following components in parts by weight: 95-105 parts of random copolymer polypropylene and 5-20 parts of the modified layered nano material.
Preferably, 0.1 to 0.2 parts of antistatic agent is also added to the PPR material. After the antistatic agent is added in the preparation process of the PPR material, the invention surprisingly discovers that the antistatic agent can play a synergistic role with the modified layered nano material in the aspects of limiting the generation and growth of cold spots, marks and bubbles on the inner and outer wall surfaces of the PPR material, not only can effectively reduce the areas of the cold spots and marks on the inner and outer wall surfaces of the PPR material, but also can reduce the bubble doubling behavior, inhibit the growth and migration of bubbles, and cooperatively improve the mechanical property and the surface quality qualification rate of the PPR material in two aspects of physics and chemistry.
Further preferably, the antistatic agent is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (SN) and/or sodium p-nonylphenoxy propyl sulfonate (NP).
The invention also provides a preparation method of the PPR material with high surface quality, which is prepared by uniformly mixing the random copolymer polypropylene, the modified layered nano material and the optional antistatic agent according to the formula amount, and carrying out melt extrusion.
Preferably, the mixing is: stirring at 60-80 deg.c for 20-30 min.
Preferably, the melt extrusion is: and adding the uniformly mixed components into a double-screw extruder, and carrying out melt extrusion.
Further preferably, the temperature of the melt extrusion is 190 to 230 ℃.
Specifically, the twin screw extruder had a first zone temperature of 170 ℃, a second zone temperature of 190 ℃, a third zone temperature of 200 ℃, a fourth zone temperature of 210 ℃, and a fifth zone temperature of 210 ℃.
The PPR material with high surface quality has less cold spots, traces and bubbles on the inner wall and the outer wall, has better mechanical property and surface quality qualification rate, and is more suitable for the fields requiring transparency, low melting point and high temperature pressure resistance, such as films, containers, pipes and the like, so that the application of the PPR material with high surface quality in preparing the films, the containers and/or the pipes is also within the protection scope of the invention.
The invention has the following beneficial effects:
when the modified layered nano material is used for modifying a PPR material, the modified layered nano material is well compatible with the PPR material, can successfully fill in molecular gaps of the PPR material to form a layered blocking structure, can reduce cold material spots and trace areas formed on the surfaces of the inner wall and the outer wall of the PPR material in the extrusion process, can not be observed by naked eyes, can also prevent bubbles from migrating to the surface, can reduce the radius of the bubbles, can inhibit the formation of bubbles visible by naked eyes, and can reduce the number of bubbles on the surfaces of the inner wall and the outer wall of the PPR material, so that the modified layered nano material can effectively improve the mechanical property and the surface quality qualification rate of the PPR material.
Drawings
FIG. 1 is a graph showing the results of the test of the FTIR values of the modified layered nanomaterials and MMT neat samples of examples 1-3.
FIG. 2 shows the test results of the modified layered nanomaterial and HT pure FTIR values of examples 8-10.
Figure 3 is an XRD pattern.
FIG. 4a is a SEM image of MMT sample, FIG. 4b is a SEM image of CTAB-MMT of example 2, FIG. 4c is a SEM image of example 1-MMT, and FIG. 4d is a SEM image of SDS-MMT of example 3.
FIG. 5a is a SEM image of HT-like material, FIG. 5b is a SEM image of CTAB-HT of example 9, FIG. 5c is a SEM image of SDS-HT of example 8, and FIG. 5d is a SEM image of 311-HT of example 10.
FIG. 6 shows the nitrogen adsorption-desorption isotherms of MMT-like and example 1-3 modified layered nanomaterials.
FIG. 7 is a graph showing pore size distribution of MMT-like modified layered nanomaterial with examples 1-3.
Fig. 8 is a nitrogen adsorption-desorption isotherm of HT pure sample and modified layered nanomaterial of examples 8 to 10.
FIG. 9 is a graph showing pore size distribution of HT samples and modified layered nanomaterials of examples 8-10.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
S1, preparing a modified layered nano material:
adding 3g of nano-scale montmorillonite powder (MMT) and 0.1g of titanate coupling agent 201 into a 50ml ball milling tank containing 8 steel balls with the diameter of 10mm and 50 steel balls with the diameter of 6mm, performing dry ball milling (ball milling for 12h at 400 rpm), washing, and performing vacuum drying to obtain a modified layered nanomaterial 201-MMT;
s2, preparing a PPR material with high surface quality:
100g of random copolymer polypropylene and 5g of modified layered nano material 201-MMT are stirred at 70 ℃ for 25min, and then added into a double screw extruder for melt extrusion, so as to obtain a PPR material with high surface quality; wherein the temperature of the first region of the twin-screw extruder is 170 ℃, the temperature of the second region is 190 ℃, the temperature of the third region is 200 ℃, the temperature of the fourth region is 210 ℃, and the temperature of the fifth region is 210 ℃.
S3, preparing dumbbell type sample bars:
preparing the PPR material with high surface quality obtained in the step S2 into standard mechanical dumbbell type sample bars through an injection molding machine; the temperature of the first area of the injection molding machine is 200 ℃, the temperature of the second area is 190 ℃, the temperature of the third area is 190 ℃, the temperature of the fourth area is 200 ℃, the pressure of the first area is 55MPa, the pressure of the second area is 50MPa, the pressure of the third area is 45MPa, and the pressure of the fourth area is 40MPa.
Example 2
The difference from example 1 is that:
(1) in S1, replacing a titanate coupling agent 201 with Cetyl Trimethyl Ammonium Bromide (CTAB), wherein the ball milling rotation speed is 500rpm, and the obtained modified layered nano material is CTAB-MMT;
(2) s2, the addition amount of the modified layered nano material is 10g.
Example 3
The difference from example 1 is that:
(1) in S1, the addition amount of MMT is 5g, 0.1g of titanate coupling agent 201 is replaced by 0.5g of Sodium Dodecyl Sulfate (SDS), dry ball milling is replaced by wet ball milling (methanol is used as a solvent), the ball milling rotating speed is 500rpm, and the ball milling time is 8h;
namely, S1 specifically comprises: adding 5g of nano-scale montmorillonite powder (MMT) and 0.5g of Sodium Dodecyl Sulfate (SDS) into a 50ml ball milling tank containing 8 steel balls with the diameter of 10mm and 50 steel balls with the diameter of 6mm, performing wet ball milling (ball milling for 8 hours at 500rpm, wherein the solvent is methanol), washing and vacuum drying to obtain a modified layered nano-material SDS-MMT;
(2) in S2, the addition amount of the modified layered nano material is 20g.
Example 4
The difference from example 3 is that: in S1, sodium Dodecyl Sulfate (SDS) is replaced by Cetyl Trimethyl Ammonium Bromide (CTAB), and the obtained modified layered nanomaterial is CTAB-MMT.
Example 5
The difference from example 1 is that: in S1, the dry ball milling was replaced with wet ball milling (methanol as solvent).
Example 6
The difference from example 5 is that: s2, the addition amount of the modified layered nano material is 10g.
Example 7
The difference from example 3 is that: in S1, sodium Dodecyl Sulfate (SDS) is replaced with a titanate coupling agent 201.
Example 8
The difference from example 2 is that: in S1, MMT was replaced with Hydrotalcite (HT), and cetyltrimethylammonium bromide (CTAB) was replaced with Sodium Dodecyl Sulfate (SDS).
Example 9
The difference from example 2 is that: in S1, MMT is replaced with Hydrotalcite (HT).
Example 10
The difference from example 2 is that: in S1, MMT is replaced with Hydrotalcite (HT), and trimethylammonium bromide (CTAB) is replaced with titanate coupling agent 311.
Example 11
The difference from example 5 is that: s2, stirring 0.1g of sodium p-nonylphenoxy propyl sulfonate (NP, purchased from Shandong Jili antistatic technology Co., ltd.) together with the random copolymer polypropylene and the modified layered nano material, and adding the mixture into a double-screw extruder for melt extrusion.
Example 12
The difference from example 2 is that: s2, 0.1g of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (SN, purchased from Nantong Chen wetting chemical Co., ltd.) is stirred together with the atactic copolymer polypropylene and the modified layered nano material, and then added into a double screw extruder for melt extrusion.
Example 13
The difference from example 3 is that: s2, stirring 0.1g of sodium p-nonylphenoxy propyl sulfonate (NP), the random copolymer polypropylene and the modified lamellar nano material together, and then adding the mixture into a double-screw extruder for melt extrusion.
Example 14
The difference from example 9 is that: s2, 0.1g of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (SN) and the random copolymer polypropylene and the modified lamellar nano material are stirred together and then added into a double-screw extruder for melt extrusion.
Comparative example 1
The difference is that in S2, modified layered nanomaterial 201-MMT is not added as in example 1.
Comparative example 2
The difference from example 2 is that in S1 MMT is not modified, i.e. MMT is used directly for the preparation of S2PPR material.
Comparative example 3
The difference from example 2 is that: in S1, the modification methods of MMT are different;
namely, S1 specifically comprises: 3g of nano-scale montmorillonite powder (MMT), 0.1g of Cetyl Trimethyl Ammonium Bromide (CTAB) and 60g of 90% (v/v) ethanol solution are added into a flask, the pH value in the flask is regulated to be 4 by glacial acetic acid, the mixture is subjected to ultrasonic treatment for 5min, reflux is carried out at 80 ℃ for 24h, and then the mixture is dried for 24h, so that modified MMT powder which is marked as CTAB-MMT is obtained.
Comparative example 4
The difference from example 3 is that: in S1, the modification methods of MMT are different;
namely, S1 specifically comprises: 5g of nano-scale montmorillonite powder (MMT), 0.5g of Sodium Dodecyl Sulfate (SDS) and 60g of 90% (v/v) ethanol solution are added into a flask, the pH value in the flask is regulated to be 4 by glacial acetic acid, the ultrasonic treatment is carried out for 5min, after refluxing for 24h at 80 ℃, the mixture is dried for 24h, and the modified MMT powder is obtained and is recorded as SDS-MMT.
Comparative example 5
The difference from example 1 is that: in S1, the modification methods of MMT are different;
namely, S1 specifically comprises: 3g of nano-scale montmorillonite powder (MMT), 0.1g of titanate coupling agent 201 and 60g of 90% (v/v) ethanol solution are added into a flask, the pH value in the flask is regulated to be 4 by glacial acetic acid, the ultrasonic treatment is carried out for 5min, the mixture is refluxed for 24 hours at 80 ℃, and then dried for 24 hours, so as to obtain modified MMT powder which is recorded as 201-MMT.
Comparative example 6
The difference from example 8 is that in S1 HT is not modified, i.e.HT is used directly for the preparation of S2PPR material.
Comparative example 7
The difference from example 8 is that in S1, the modification method of HT is different;
namely, S1 specifically comprises: 3g of Hydrotalcite (HT), 0.1g of Sodium Dodecyl Sulfate (SDS) and 60g of 90% (v/v) ethanol solution were added to a flask, the pH value in the flask was adjusted to 4 with glacial acetic acid, the mixture was sonicated for 5min, refluxed at 80℃for 24 hours, and dried for 24 hours to obtain a modified MMT powder, which was designated SDS-HT.
Comparative example 8
The difference from example 9 is that in S1, the modification method of HT is different;
namely, S1 specifically comprises: 3g of Hydrotalcite (HT), 0.1g of cetyltrimethylammonium bromide (CTAB) and 60g of 90% (v/v) ethanol solution were added to a flask, the pH value in the flask was adjusted to 4 with glacial acetic acid, the mixture was sonicated for 5min, refluxed at 80℃for 24 hours, and then dried for 24 hours, to obtain a modified MMT powder, designated CTAB-HT.
Comparative example 9
The difference is that in S2, no modified layered nanomaterial is added as in example 13.
Comparative example 10
The difference from example 11 is that in S1, the modification method of MMT is different;
namely, S1 specifically comprises: 3g of nano-scale montmorillonite powder (MMT), 0.1g of titanate coupling agent 201 and 60g of 90% (v/v) ethanol solution are added into a flask, the pH value in the flask is regulated to be 4 by glacial acetic acid, the ultrasonic treatment is carried out for 5min, the mixture is refluxed for 24 hours at 80 ℃, and then dried for 24 hours, so as to obtain modified MMT powder which is recorded as 201-MMT.
Comparative example 11
The difference from example 12 is that in S1, the modification method of MMT is different;
namely, S1 specifically comprises: 3g of nano-scale montmorillonite powder (MMT), 0.1g of Cetyl Trimethyl Ammonium Bromide (CTAB) and 60g of 90% (v/v) ethanol solution are added into a flask, the pH value in the flask is regulated to be 4 by glacial acetic acid, the mixture is subjected to ultrasonic treatment for 5min, reflux is carried out at 80 ℃ for 24h, and then the mixture is dried for 24h, so that modified MMT powder which is marked as CTAB-MMT is obtained.
Comparative example 12
The difference from example 13 is that: in S1, the modification methods of MMT are different;
namely, S1 specifically comprises: 5g of nano-scale montmorillonite powder (MMT), 0.5g of Sodium Dodecyl Sulfate (SDS) and 60g of 90% (v/v) ethanol solution are added into a flask, the pH value in the flask is regulated to be 4 by glacial acetic acid, the ultrasonic treatment is carried out for 5min, after refluxing for 24h at 80 ℃, the mixture is dried for 24h, and the modified MMT powder is obtained and is recorded as SDS-MMT.
Comparative example 13
The difference from example 14 is that: in S1, HT modification methods are different;
namely, S1 specifically comprises: 3g of Hydrotalcite (HT), 0.1g of cetyltrimethylammonium bromide (CTAB) and 60g of 90% (v/v) ethanol solution were added to a flask, the pH value in the flask was adjusted to 4 with glacial acetic acid, the mixture was sonicated for 5min, refluxed at 80℃for 24 hours, and then dried for 24 hours, to obtain a modified MMT powder, designated CTAB-HT. Test example 1 FTIR analysis of modified layered nanomaterials
KBr pellet was used as background test and then pellet test was performed. The tablet is pressed according to the following proportion of 50:1, mixing KBr powder and samples (modified layered nano materials of examples 1-3 and 8-10, MMT pure sample and HT pure sample) in a mortar made of agate, pressing into transparent flakes in a tablet press, and finally placing the pressed flakes in an FTIR instrument for testing the FTIR value. The test results of the modified layered nanomaterial and MMT-like FTIR values of examples 1 to 3 are shown in fig. 1, and the test results of the modified layered nanomaterial and HT-like FTIR values of examples 8 to 10 are shown in fig. 2.
As can be seen from FIG. 1, the MMT sample is 3442-3629 cm -1 Hydroxyl stretching vibration peak of interlayer adsorbed water is 1644cm -1 The hydroxyl bending vibration peak of the interlayer crystallization water appears at the position of 1036cm -1 Si-O skeleton absorption peaks appear at the positions; in addition, the 201-MMT of example 1 was between 2859 and 2932cm, except for the characteristic peaks inherent to MMT -1 CTAB-MMT of example 2 at 2852-2921 cm -1 SDS-MMT of example 3 at 2853-2922 cm -1 All also present-CH 3 and-CH 2 The antisymmetric and symmetrical telescopic vibration peaks of the montmorillonite indicate that the montmorillonite is successfully modified, and the modifier is successfully entered between silicate sheets of the montmorillonite.
As can be seen from FIG. 2, the HT purity is 2850-2924 cm -1 Hydroxyl stretching vibration peak of interlayer adsorbed water appears in the interlayer, 671cm -1 Is CO 3 2- Is 462cm -1 Is a characteristic peak of HT skeleton structure. In addition, SDS-HT of example 8, CTAB-HT of example 9 and 311-HT of example 10 were all between 2850 and 2924cm, except for characteristic peaks inherent to HT -1 where-CH 3 and-CH 2 Is enhanced by the antisymmetric and symmetrical stretching vibration peaks of 671cm -1 CO of (c) 3 2- The peak is weakened, which initially indicates that the hydrotalcite is successfully modified, and the modifier successfully enters the silicate interlayer of the hydrotalcite.
Test example 2 XRD analysis of modified layered nanomaterial
In order to investigate whether the modifier successfully enters the MMT sheet, XRD tests were performed on the modified layered nanomaterial and MMT pure sample of examples 1-3 by using a K-Alpha X-ray diffractometer of the company Siemens Feier, under the following measurement conditions: the CuKa is taken as a ray source, the voltage is 40kV, the current is 40mA, and the scanning angle is 3-80 degrees.
The XRD patterns measured are shown in FIG. 3. From fig. 3 and Bragg equation 2dsin θ=λ, it can be calculated that: the interlayer spacing d=1.52 nm of the example 1-MMT, the interlayer spacing d=1.36 nm of the example 2CTAB-MMT, and the interlayer spacing d=1.48 nm of the example 3SDS-MMT are all significantly larger than the interlayer spacing (d=1.05 nm) of the unmodified MMT, which indicates that the modifier successfully enters the interlayer of the MMT, increases the interlayer spacing of the MMT, and is more beneficial to filling the molecular gaps of the PPR material in the later period to form a layered barrier structure.
Test example 3 SEM analysis of modified layered nanomaterial
The modified layered nano materials, MMT pure samples and HT pure samples of examples 1-3 and 8-10 are dried and uniformly distributed on a conductive adhesive tape, and after gold spraying for 60s treatment, the morphology of the samples is observed through SEM and photographed. The results are shown in FIG. 4 and FIG. 5, wherein FIG. 4a is an SEM image of the pure MMT, FIG. 4b is an SEM image of example 2CTAB-MMT, FIG. 4c is an SEM image of example 1 201-MMT, FIG. 4d is an SEM image of example 3SDS-MMT, FIG. 5a is an SEM image of the pure HT, FIG. 5b is an SEM image of example 9CTAB-HT, FIG. 5c is an SEM image of example 8SDS-HT, and FIG. 5d is an SEM image of example 10-HT.
As can be seen from fig. 4, the unmodified MMT is in the form of a sheet block with no curling of the end face; the 201-MMT of example 1 is curled in edge and loose in whole and easy to disperse, the CTAB-MMT of example 2 and the SDS-MMT of example 3 are in small blocks, and the dispersibility is improved, which shows that part of modifier successfully enters the intercalation of MMT, the hydrophilic effect of hydroxyl groups on the surface of MMT is reduced, so that the MMT is not easy to accumulate, and the XRD result is consistent.
As can be seen from fig. 5, unmodified HT is in a near spherical and irregular aggregation state; whereas SDS-HT of example 8, CTAB-HT of example 9, 311-HT of example 10, in addition to retaining the original near-spherical structural features of unmodified HT, were also surface coated with some Xu Sirong-like filaments, which may be that the modifier adsorbed surrounding nano-scale hydrotalcite particles, initially demonstrating successful attachment of the modifier to the hydrotalcite surface.
Test example 4 BET analysis of modified layered nanomaterial
Test samples (modified layered nanomaterial, MMT pure sample, HT pure sample of examples 1-3 and 8-10) were tested for specific surface area and pore structure using Tristar II3020 type full-automatic specific surface and porosity analysis physical adsorption instrument (Mimerorelix Corp.) at-195℃and N was selected 2 As an adsorption gas. The N obtained 2 The adsorption-desorption isotherms and the BJH pore size distributions are shown in fig. 6 to 9, wherein fig. 6 is a nitrogen adsorption-desorption isotherm of the MMT pure sample and the modified layered nanomaterial of examples 1 to 3, fig. 7 is a pore size distribution diagram of the MMT pure sample and the modified layered nanomaterial of examples 1 to 3, fig. 8 is a nitrogen adsorption-desorption isotherm of the HT pure sample and the modified layered nanomaterial of examples 8 to 10, and fig. 9 is a pore size distribution diagram of the HT pure sample and the modified layered nanomaterial of examples 8 to 10.
As can be seen from FIGS. 6 and 7, the 201-MMT of example 1, the CTAB-MMT of example 2, the SDS-MMT of example 3 and the unmodified MMT all belong to the class IV isotherms in the nitrogen adsorption-desorption isotherms, and the relative pressure (P/P 0 ) 0.45 to 1.0P/P 0 The diapause rings are all in the range, and belong to H3 type diapause rings, which shows that the pore structures of MMT and modified layered nano materials are plate-shaped and slit-shaped, which are consistent with the layered structure of montmorillonite, are mesoporous structures, and the pore diameters of the four materials are all distributed between 10 nm and 70nm, especially about 20 nm. In addition, the 201-MMT of example 1 has a nitrogen adsorption amount and a pore volume > MMT in the range of relative pressure 0 to 1.0, because the titanate coupling agent 201 increases the interlayer spacing of MMT; the CTAB-MMT of example 2 and the SDS-MMT of example 3 are both < MMT in the range of relative pressure 0 to 1.0, because CTAB and SDS occupy the pore structure of montmorillonite, resulting in a decrease in adsorption amount and pore capacity.
As can be seen from FIGS. 8 and 9, SDS-HT of example 8, CTAB-HT of example 9, 311-HT of example 10 and unmodified HT all have typical IV isotherms in the nitrogen adsorption-desorption isotherms, and the hysteresis loop belongs toH3 type shows that HT and modified layered nano material are mesoporous material, slit-shaped pores produced by aggregation of particles, and the pore diameters of the four materials are distributed between 5 and 90 nm. In addition, the coexistence adsorption-desorption curve of the modified layered nano material is close to P/P 0 When=1, the pressure rises to a higher relative pressure value, which indicates that the modified layered nanomaterial has a porous structure in which mesopores and macropores coexist. The specific surface area and pore volume and pore diameter of the modified layered nanomaterial are both higher than those of unmodified hydrotalcite, probably because the modifier adsorbs surrounding nano HT, and the specific surface area and pore diameter of HT are increased.
Test example 5 oil absorption and contact Angle test of modified layered nanomaterial
The modified layered nano-materials of examples 1 to 10 and comparative examples 2 to 8 were tested for oil absorption and contact angle, and the results are shown in table 1. The finer the powder of the modified layered nano material (related to BET test characterization) and the higher the dispersity (related to SEM test characterization), the larger the oil absorption value, the more oleophilic the material, and the better the compatibility with PPR, thereby improving the tensile and impact properties of the PPR material. The contact angle is the same as the oil absorption value, and the larger the contact angle is, the more hydrophobic the material is, the more easily the material is compatible with the hydrophobic PPR, so that the tensile and impact properties of the PPR material are improved.
Table 1 oil absorption and contact angle of modified layered nanomaterial
| Sequence number | Filler ingredient ratio/part | Oil absorption value/g | Contact angle/° |
| Example 1 | MMT：201＝3：0.1 | 0.45 | 44.398 |
| Example 2 | MMT：CTAB＝3：0.1 | 0.42 | 42.359 |
| Example 3 | MMT：SDS＝5：0.5 | 0.49 | 51.591 |
| Example 4 | MMT：CTAB＝5：0.5 | 0.48 | 50.066 |
| Example 5 | MMT：201＝3：0.1 | 0.51 | 53.778 |
| Example 6 | MMT：201＝3：0.1 | 0.43 | 42.752 |
| Example 7 | MMT：201＝5：0.5 | 0.52 | 55.826 |
| Example 8 | HT：SDS＝3：0.1 | 0.53 | 60.753 |
| Example 9 | HT：CTAB＝3：0.1 | 0.54 | 65.453 |
| Example 10 | HT：311＝3：0.1 | 0.56 | 70.325 |
| Comparative example 2 | MMT | 0.33 | 35.543 |
| Comparative example 3 | MMT：CTAB＝3：0.1 | 0.39 | 39.158 |
| Comparative example 4 | MMT：SDS＝5：0.5 | 0.40 | 39.952 |
| Comparative example 5 | MMT：201＝3：0.1 | 0.41 | 41.507 |
| Comparative example 6 | HT | 0.38 | 39.001 |
| Comparative example 7 | HT：SDS＝3：0.1 | 0.41 | 41.751 |
| Comparative example 8 | HT：CTAB＝3：0.1 | 0.40 | 39.897 |
As can be seen from table 1:
(1) The oil absorption and contact angle of example 1 were greater than those of chemically modified comparative example 5, the oil absorption and contact angle of example 2 were greater than those of unmodified comparative example 2, chemically modified comparative example 3, the oil absorption and contact angle of example 3 were greater than those of chemically modified comparative example 4, the oil absorption and contact angle of example 8 were greater than those of unmodified comparative example 6, chemically modified comparative example 7, the oil absorption and contact angle of example 9 were greater than those of chemically modified comparative example 8, and the oil absorption and contact angles of examples 11 to 14 were sequentially greater than those of chemically modified comparative examples 10 to 13. It is shown that the invention adopts a specific modification method, namely ball milling modification, so that the particle size of the layered nano material is smaller, DOP can be promoted to enter, the oil absorption value is increased, and meanwhile, the action sites of the modifier and the layered nano material can be increased, so that the modifier and the layered nano material can better interact, the surface tension is reduced, the contact angle is increased, the obtained modified layered nano material can be better compatible with PPR, and the mechanical property of the PPR material is effectively improved.
(2) The oil absorption value and the contact angle of example 5 (wet ball milling) are both greater than those of example 1 (dry ball milling), indicating that wet ball milling can more effectively improve the oil absorption value and the hydrophobicity of the layered nanomaterial. .
(3) The oil absorption and contact angle of example 3 (SDS) were both greater than those of example 4 (CTAB), indicating that SDS increased the oil absorption and hydrophobicity of MMT more than CTAB when MMT was modified by dry ball milling.
(4) The oil absorption and contact angle of example 7 (titanate coupling agent 201) were both greater than that of example 3 (SDS), indicating that titanate coupling agent 201 is more capable of increasing the oil absorption and hydrophobicity of MMT than SDS when MMT is modified by dry ball milling.
(5) The oil absorption value and the contact angle of the example 9 (HT) are both larger than those of the example 2 (MMT), which shows that the compatibility of the HT and the PPR material is better than that of the MMT, and the mechanical property of the PPR material can be improved.
(6) The oil absorption and contact angle of example 9 (CTAB) were both greater than that of example 8 (SDS), indicating that CTAB is more capable of increasing the oil absorption and hydrophobicity of HT than SDS when HT is modified by dry ball milling.
(7) The oil absorption and contact angle of example 10 (titanate coupling agent 311) were both greater than that of example 9 (CTAB), indicating that titanate coupling agent 311 is more capable of increasing the oil absorption and hydrophobicity of HT than CTAB when HT is modified by dry ball milling.
Test example 6 surface quality and mechanical Property test of dumbbell-shaped sample bars
The dumbbell-shaped bars of examples 1 to 14 and comparative examples 1 to 13 were observed for smoothness of the inner and outer wall surfaces and for the presence of cold spots, marks and bubbles according to the following conditionsCalculate the surface quality yield (wherein, W Failure to pass The number of the sample bars with one or more unqualified phenomena of unsmooth, cold material spots, marks or bubbles is indicated, W Qualified product Refers to the number of bars that are completely free of the aforementioned failure. Tensile properties of the dumbbell-shaped bars of examples 1 to 14, comparative examples 1 to 13 were tested according to GB/T1040..2-2006 at a rate of 50mm/min and impact properties were tested according to GB/T8809-2015, the results of which are shown in Table 2.
TABLE 2 surface quality and mechanical Property test results of dumbbell type sample bars
As can be seen from table 2:
(1) The surface quality percent of pass, tensile properties and impact properties of example 1 were all superior to those of chemically modified comparative example 5, the surface quality percent of pass, tensile properties and impact properties of example 2 were all superior to those of unmodified comparative example 2, chemically modified comparative example 3, the surface quality percent of pass, tensile properties and impact properties of example 3 were all superior to those of chemically modified comparative example 4, the surface quality percent of pass, tensile properties and impact properties of example 8 were all superior to those of unmodified comparative example 6, chemically modified comparative example 7, the surface quality percent of pass, tensile properties and impact properties of example 9 were all superior to those of chemically modified comparative example 8, and the surface quality percent of pass, tensile properties and impact properties of examples 11 to 14 were all superior to those of chemically modified comparative examples 10 to 13. The invention is characterized in that the mechanical property and the surface quality qualification rate of the PPR material can be effectively improved only by adopting a specific modification method, namely ball milling modification.
(2) The surface quality qualification rate, tensile property and impact property of the example 5 (wet ball milling) are all superior to those of the example 1 (dry ball milling), which shows that the wet ball milling can more effectively improve the mechanical property and the surface quality qualification rate of the PPR material.
(3) The surface quality qualification rate, tensile property and impact property of the SDS of the example 3 (SDS) are all superior to those of the example 4 (CTAB), which shows that the SDS can more effectively improve the mechanical property and the surface quality qualification rate of the PPR material than the CTAB when the MMT is modified by dry ball milling.
(4) The surface quality qualification rate, tensile property and impact property of the titanate coupling agent 201 of the embodiment 7 are all superior to those of the embodiment 3 (SDS), which shows that the titanate coupling agent 201 can more effectively improve the mechanical property and the surface quality qualification rate of the PPR material than the SDS when the MMT is modified by dry ball milling.
(5) The surface quality qualification rate, tensile property and impact property of the example 9 (HT) are all better than those of the example 2 (MMT), which shows that the compatibility of the HT and the PPR material is better than that of the MMT, and the mechanical property and the surface quality qualification rate of the PPR material can be more effectively improved.
(6) The surface quality qualification rate, tensile property and impact property of example 9 (CTAB) are all superior to those of example 8 (SDS), which shows that CTAB can more effectively improve the mechanical property and surface quality qualification rate of PPR material than SDS when HT is modified by dry ball milling.
(7) The surface quality qualification rate, tensile property and impact property of the example 10 (the titanate coupling agent 311) are all better than those of the example 9 (CTAB), which shows that the titanate coupling agent 311 can more effectively improve the mechanical property and the surface quality qualification rate of the PPR material than the CTAB when the HT is modified by dry ball milling.
(8) The surface quality qualification rate, the tensile property and the impact property of the example 11 are all better than those of the example 5, the surface quality qualification rate, the tensile property and the impact property of the example 12 are all better than those of the example 2, the surface quality qualification rate, the tensile property and the impact property of the example 13 are all better than those of the example 3, and the surface quality qualification rate, the tensile property and the impact property of the example 14 are all better than those of the example 9, so that the antistatic agent can enable the modified layered nano material to be more compatible with the PPR, and the mechanical property and the surface quality qualification rate of the PPR material can be more effectively improved.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. The PPR material with high surface quality is characterized by comprising the following components in parts by weight: 95-105 parts of random copolymer polypropylene, 5-20 parts of modified layered nano material and 0.1-0.2 part of antistatic agent;
wherein the antistatic agent is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and/or sodium p-nonylphenoxy propyl sulfonate; the modified layered nano material is obtained by ball milling montmorillonite and titanate coupling agent 201 or hydrotalcite and titanate coupling agent 311.
2. The PPR material according to claim 1, wherein the mass ratio of montmorillonite to titanate coupling agent 201 is 3-5: 0.1 to 0.5.
3. The PPR material according to claim 1, wherein the mass ratio of hydrotalcite to titanate coupling agent 311 is 3-5: 0.1 to 0.5.
4. The PPR material according to claim 1, wherein said ball milling is performed at 400-500 rpm for 8-24 hours.
5. The method for preparing the PPR material with high surface quality according to any one of claims 1 to 4, which is characterized in that the preparation method comprises the steps of uniformly mixing the random copolymer polypropylene, the modified layered nano material and the antistatic agent according to the formula amount, and carrying out melt extrusion;
wherein the antistatic agent is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and/or sodium p-nonylphenoxy propyl sulfonate; the modified layered nano material is obtained by ball milling montmorillonite and titanate coupling agent 201 or hydrotalcite and titanate coupling agent 311.
6. Use of the high surface quality PPR material according to any one of claims 1 to 4 for the preparation of films, containers and/or pipes.
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| CN1473872A (en) * | 2002-08-08 | 2004-02-11 | 马晓燕 | Rectorte/polypropylene nano comoposite material and its preparing method |
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| CN1473872A (en) * | 2002-08-08 | 2004-02-11 | 马晓燕 | Rectorte/polypropylene nano comoposite material and its preparing method |
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